• Volume 32,Issue 11,2015 Table of Contents
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    • >Biological engineering
    • Preparation of gluconic acid by enzymic process coupled with in situ product removal

      2015, 32(11).

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      Abstract:The glucose oxidase and catalase immobilized in polyvinyl alcohol and sodium alginate matrix as biocatalyst for conversion of glucose to gluconic acid in bubbling reactor coupled with in situ product removal was investigated. The conversion was inhibited by glucose acid. Using the D335 resin, which has good adsorption capacity of gluconic acid, could relieve the inhibition. By the fed batch- in situ removal, gluconic acid conversion can reach 95.5%. The system was stable, it could successively convert for four cycles, and the average conversion was more than 85.7%.

    • >Oil field chemicals and petroleum additives
    • The Preparation and Low Fluid Loss Performance of Hydroxypropyl Starch

      2015, 32(11).

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      Abstract:bstract:The preparation techniques of hydroxypropyl starch(HPS) by half-dry method and solvent method were introduced, and the low fluid loss performance was studied and compared. The result shows that half-dry method was a good method. The optimum reaction conditions were as follows: reaction temperature 55℃, reaction time 8h, the ratio of m(sodium hydroxide) to m(starch) 0.014, the ratio of m(propylene oxide) to m(starch) 0.30, water content in reaction system 31%, The MS of product is 0.33. The product could resist temperature up to 150℃ in 4% NaCl salt water muds, while the product made by solvent method only to 140℃. Compared with solvent method product at 140℃, it has excellent capacities of salts , and could be used in saturated-salt solution, the maximum content of Ca2+ and Mg2+ was 930mg/L and 360mg/L, respectively. Further studies show that the product had a good low fluid loss performance when MS is over 0.2. The fluid loss performance of HPS is related to the MS and the synthesis process.

    • >Fine chemical intermediates
    • Synthesis and Property Evaluation of New Imidazoline Amide Inhibitor

      2015, 32(11).

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      Abstract:Abstract: Aiming at the phenomenon that the corrosion of overhead circulating reflux of fractionating tower aggravates in processing crude oil with high acid value, new imidazoline amide called EYP was synthesized from oleic acid, diethylene triamine and acetic anhydride. The synthesized compound was characterized by 1H-NMR and FT-IR and the thermostability was investigated by thermogravimetric analysis. The inhibition efficiency of EYP in simulated oil was evaluated by weight loss measurement in comparison with commercially available corrosion inhibitors. Besides, the corrosion morphology of mild steel surface was analyzed by SEM. The results showed that the structure of this compound was correct and that its thermal stability was also good. It had a good inhibition efficiency for A3 mild steel in simulative oil and was a new efficient corrosion inhibitor with high stability and low-cost.

    • >Drug and cosmetic materials
    • Synthesis of Veratramine Analogs and Evaluation of their antiproliferative activities on cancer cell in vitr

      2015, 32(11).

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      Abstract:In this study, the steroidal alkaloid veratramine, which is rich in Veratrum plants, was taken as the starting material for structure modification. Five veratramine analogs 2~6 were obtained. Their structures were determined by means of MS and NMR. Cyclopamine, the first inhibitor of Hedgehog signaling pathway, was used as the positive control, and the antiproliferative activities of yielded compounds on human grastric cancer cell SGC-7901 and human pancreatic cancer cell Aspc-1 in vitro were carried out. The results showed that the antiproliferative activities of compounds 4, 5 and 6 were much more potent than that of cyclopamine. Preliminary study of the structure-activity relationship suggested that antiproliferative activities of veratramine analogs could be increased by introducing appropriate hindering groups at piperidine ring of veratramine.

    • Preparation,characterization of AlH3P2W18O62?nH2O/MCM-41 and its activity on catalytic synthesis of aspirin

      2015, 32(11).

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      Abstract:A series of dawson type aluminiumphosphotungstates supported on MCM-41 molecular sieve(AlH3P2W18 O62?nH2O/MCM-41)were prepared by immersion process and was used in the synthesis of acetylsalicylic. The structures of catalysts were characterized by FT-IR, XRD, SEM , EDX, BET, NH3-TPD,N2-TPD and TG-DSC. Influences of amount of AlH3P2W18O62?nH2O loading, dosage of catalyst, the mole ratio of reactants, reaction temperature, reaction time and reusability of catalyst on the reaction were investigated. The results indicated that the AlH3P2W18O62?nH2O was evenly loaded on the MCM - 41 carrier and existed in the form of Dawson structure. Compared with AlH3P2W18O62?nH2O, the high specific surface area and thermal stability of supported catalyst (30% AlH3P2W18O62?nH2O/MCM-41) increased, but the acid strength of supported catalyst reduced. The supported catalyst showed honeycomb shape and had both Br?nsted and Lewis acid centers. Under the optimal conditions,i.e, loading amount of AlH3P2W18O62?nH2O of 30%, w (30% AlH3P2W18 O62?nH2O/MCM-41)=4.1% (relative to the dosage of total reactant), reaction temperature of 80℃, reaction time of 30 min, the yield of aspirin could reach 96.3%. The catalyst has good reusability and the yield of aspirin could reach 80.6% after six cycles. 30% AlH3P2W18 O62?nH2O /MCM-41 is the efficient and environmental friendly catalyst in synthesizing aspirinwith good catalytic activity and reusability.

    • >Leather chemicals
    • Synthesis and Characterization of Waterborne Polyurethane Modified by Collagen based on Waste Leather

      2015, 32(11).

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      Abstract:The isophorone diisocyanate , polytetra hydrofuran, 1, 4—butanediol, dimethylolpropionic acid were used as raw materials, and the waterborne polyurethane emulsion modified by collagen was synthesized by a prepolymer process. The collagen extracted from waste leather as a modifier was added during the process of synthesis, and the effect of collagen dosage on the emulsion and film was studied systematically and the structure of polyurethane film was characterized by FTIR, XRD and AFM. The results showed that the collagen was grafted on the main chain of polyurethane. The particle size of polyurethane emulsion and the crystallization trend of polyurethane film increased as the addition of collagen, while the surface roughness of film decreased. The optimal dosage of collagen was 10 % of the total quality of IPDI and PTMG, and the mechanical properties and water resistance of polyurethane film were optimal. The tensile index of film was 10.20 Mpa, 11.61 % higher than that of blank sample. The water absorption of film was 2.25 %, reduced by 87.82 % than the blank sample.

    • >Surfactants
    • Synthesis and Performance of Sulfoxide-modified Methionine Surfactants

      2015, 32(11).

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      Abstract:Four sulfoxide-modified methionine surfactants with different carbon chain length were synthesized from long chain fatty acid and methionine as staring materials. Then, the structure of the products were characterized by means of FTIR, 1HNMR and ESI-MS, and the surface tension, critical micelle concentrations (CMC), emulsifying property, foaming property, hard water stability and antibacterial activity were investigated. The results show that the minimum surface tension of surfactant in this series are below 25 mN/m, the CMC of less than 1 g/L. Moreover, it is indicated that the four kinds of product all have good antibacterial activity against Escherichia coli, Staphylococcus aureus and Candida albicans .

    • >Functional materials
    • Performance testing of VMT/P(AMPS-co-AA) superabsorbent composite

      2015, 32(11):0-0.

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      Abstract:The effect of pH and salts concentration on the equilibrium swelling of the vermiculite/poly(2-acrylamido-2-methyl-1-propanesulfonic acid-co-acrylic acid) (VMT/P(AMPS-co-AA)) superabsorbent composite prepared by glow discharge electrolysis plasma (GDEP) were studied systematically. Factors influencing the adsorption of superabsorbent composite for cationic dyes such as pH, adsorption time, dye concentration were investigated in detail by batch experiments. Adsorption-desorption properties of materials were studied as well. The results showed that the superabsorbent composite has pH sensitivity, salt sensitivity, high water absorbency and adsorption capacity. The maximum equilibrium swelling ratio of the superabsorbent composite in distilled water is 822.4 g/g. The maximum adsorption capacities of the superabsorbent composite for Methylene blue (MB), Crystal violet (CV) and Malachite green (MG) are 2027.8, 2171.8 and 883.2 mg/g, respectively. The adsorption process of dyes follows the pseudo-second-order kinetic model with multi-step diffusion process at pH=6.5 and 25. In addition, VMT/P(AMPS-co-AM) hydrogel has certain adsorption-desorption performance, and can be also regenerated and reused.

    • >Surfactants
    • Surface Activities and Application Performances of Dodecyl Trimethyl Ammonium Hydroxide and Alkyl Polyglycoside Surfactant Mixtures

      2015, 32(11).

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      Abstract:The stability, surface activities and application performances of dodecyl trimethyl ammonium hydroxide (DTAH) and alkyl polyglycoside surfactant mixed systems were measured. The results show that the transmittance of mixtures over 80% when the active matter content of mixtures below 70 g/L, indicate the mixtures show good stability. The critical micelle concentration and surface tension of mixtures have lower value than single surfactant solution. And the mixtures show better foaming abilities, emulsifying properties, wetting properties and clearing power than DTAH.

    • >Biological engineering
    • Enhancing Acetone Synthesis by Co-culturing C. acetobutylicum/S. cerevisiae Integrated with Exogenous Acetate Addition: Life Cycle Assessment Emphasized ABE Fermentation

      2015, 32(11).

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      Abstract:Proposed a novel fermentation strategy of co-culturing C. acetobutylicum/S. cerevisiae integrated with exogenous acetate addition, to enhance acetone and butanol productions simultaneously. Compared with control group, concentrations of butanol and acetone, as well as acetone/butanol ratio reached high levels of 13.91 g/L, 8.27 g/L and 0.59, respectively; with the increments of 19.6%, 41.1% and 18.0%, when adding the synthetic acetate. On the other hand, the relevant fermentation indexes also reached 14.23 g/L, 8.55 g/L and 0.60, respectively, with the increments of 22.4%, 46.0% and 20.0%, when directly adding the cheaper acetate fermentative supernatant, resulting a reduced raw materials cost and enhanced industrial ABE fermentation feasibility. Results show that the proposed strategy could stimulate secretions of the four amino acids, which were beneficial for C. acetobutylicum survival and butanol synthesis; moderately repress NADH regeneration and reduce the cellular energy load. These led to an enhanced acetone synthesis but without sacrificing butanol production, and entire ABE fermentation performance was significantly improved.

    • >Modernization technology of traditional Chinese medicines
    • Study on purification technology of total flavonoids from Indocalamus leaves with polyamide resin

      2015, 32(11).

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      Abstract:By using single factor and orthogonal experiments, the optimum conditions in the purification of total flavonoids from Indocalamus leaves with polyamide resin were studied. The results showed that the optimal sample condition was 2.60 mg•mL-1 in sample concentration, 20 mL of sample volume, sample flow rate of 1.0 mL•min-1, and the optimum elution condition was eluent of 80%(V/V) ethanol, elution liquid amount of 150 mL, the elution rate of 0.5 mL•min-1, the average desorption rate could run up to 94.54%,the amount and concentration of the eluent were significant factors. flavonoids, flavonols and isoflavones could be identified in color reaction of gradient elution.

    • Optimization of Ultrasonic-assisted Extraction of Tannin from Persimmon Veneer and Their Antioxidation Activity

      2015, 32(11).

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      Abstract:Using ethanol as extraction solvent, tannin was extracted under ultrasonic assistance from persimmon veneer. The optimal ultrasonic-assisted extraction technology was determined by single factor experiment and orthogonal experiment; The antioxidant activity of crude extract and purification were determined by POV measured values and the absorbance values of MDA. The results show that The optimum values of extraction parameters including ethanol ratio, extraction power, extraction temperature and length of extraction were determined by orthogonal array design to be: 50%, 360 W, 70 癈,50 min and the tannin yield was 5.6%. Both the crude extract and purification have antioxidant activity, with an antioxidant sequence of purification > crude extract. Especially, the higher purity had better antioxidant activity . The crude extract exhibits antioxidation for oil when the dosage is 0.08 %, but and it hasn’t synergistic action with VC. 0.04 % purification had good antioxidant effect which is better than VC, but it hasn’t synergistic action with VC.

    • >Catalysis,separation and purification technology
    • Adsorption Kinetics and Thermodynamics of SO42- on D201 Resin and Characterization Analysis

      2015, 32(11).

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      Abstract:The D201 macroreticular polystyrene strong base ion exchange resin was applied to SO42 - adsorption removal from wastewater, which adsorption kinetics and thermodynamic were analyzed. The resins before and after adsorption were characterized by XRD, FTIR and SEM, the adsorption mechanism was also discussed. The results show that the adsorption process conforms to the pseudo-second order kinetic model, qe'= 63.291 mg/g (qe= 62.585 mg/g), liquid film diffusion is the controlling step, and the diffusion constant is 0.1623, rapid agitation or bigger bore diameter of resin can obtain faster response speed; Langmuir isotherm fits better to the adsorption behavior, which is monolayer adsorption and favorable adsorption for D201 resin, the adsorption process is endothermic process; the characterization shows that D201 resin is amorphous substance with much activity and many micro- and macro-pores on the surface, and became more clear and smooth after adsorption. The characteristic peak of SO3H— also appeared, as a result of the reaction of SO42-and [—N(CH3)3OH] on D201 resin.

    • Synthesis of 14-Alkyl- or Aryl-14H-Dibenzo[a,j]xanthenes Catalyzed by β-Cyclodextrin-Propyl Sulfonic Acid

      2015, 32(11).

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      Abstract:β-CD was reacted with 1, 3-propane sultone in NaOH solution to afford sulfopropyl ether β-cyclodextrin, and subsequently, it was further treated with acidic resin to give β-cyclodextrin-propyl sulfonic acid (β-CD-PSA). In order to optimize the conditions, the condensation reaction of benzaldehyde and β-naphthol was examined in presence of different amounts of β-CD-PSA under various reaction conditions. A series of 14-alkyl- or aryl-14H-dibenzo[a,j]xanthenes were synthesized in presence of 1 mol% of β-CD-PSA, in water at 100 ℃ to afford the corresponding compounds in 85~95% within 6~60 min. The catalyst can be reusable. It could be reused ten-times without a significant loss of catalytic activity. The present protocol offers several advantages, including simple work-up procedure, high yields, short reaction time and benignity procedure.

    • Crystallization Process Studies of Carbamazepine

      2015, 32(11).

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      Abstract:Crystallization process of carbamazepine (CBZ) polymorphs was investigated using the biomicroscope, X-ray powder diffraction (XRD), Malvin particle analysis, DSC and FBRM and PVM. The effect of different operation factors such as solvents, seeds, crystallization method, drying, temperature, agitation rate and cooling rate on the properties, especially the polymorph of carbamazepine were investigated. The results show that CBZ dihydrate could be recrystallization from ethanol-water mixture, CBZ form III could be obtained through slow cooling in alcohol solvents, CBZ form II was got by recrystallization in THF. The conformity of the particle could be obtained by adding large amount of fine seeds. The CBZ form II was easy to include solvent because its special structure (the channel). The temperature play a mainly role for the polymorph of CBZ, it gave CBZ form III a lower temperature range (52~20℃), while gave CBZ form II a higher temperature range(90~76℃). The mean particle size was easy to obtain when the stirring rate was higher.The cooling rate didn’t affect the polymorph of CBZ, all the products were CBZ form III, but there was a difference in crystal size distribution (CSD).

    • >Perfumes and essences
    • Comparative Analysis of Free Amino Acid Composition and Taste Contribution in Four Kinds of Chicken Soup

      2015, 32(11).

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      Abstract:In order to analyze the composition and the TAV of free amino acids in Beijing Fatty chicken soup, Sanhuang chicken soup, Benpao chicken soup and Sanyang chicken soup, the chicken soup was cooked, centrifugaled and freezing dried, the free amino acid in chicken soup was detected by automatic analyzer. 17 kinds of free amino acid were isolated in four kinds of chicken soup, of which there were seven kinds of essential amino acids, and the content of histidin is the highest one in four kinds of chicken soup. Sanyang chicken soup had the highest total content of free amino acid (46.47 mg/mL), and the lowest one was Sanhuang chicken soup (16.86 mg/mL).The total content of essential amino acid content was the highest in Sanyang chicken soup (10.02 mg/mL), and Sanhuang chicken soup had the least content of one (3.88 mg/mL). There were 9 kinds of bitter taste amino acids, 2 kinds of umami amino acids and 5 kinds of sweet amino acids in 4 kinds of chicken soup. The content of umami amino acid in Sanhuang chicken soup was higher than other groups (18.53%). The content of sweet amino acid in Benpao chicken soup was the highest (30.42%). According to the results of amino acid taste active values (TAV), Beijing Fatty chicken soup has 11 kinds of amino acids which had taste contribution to soup, Sanhuang chicken soup have 6 kinds, Benpao chicken soup have 10 kinds, Sanyang chicken soup have 11 kinds. PCA analysis and discrimination index results by electronic tongue showed that minimum differences is Benpao chicken soup and Sanhuang soup, the largest is the Sanyang chicken soup and Beijing Fatty chicken soup.

    • >Electro-organic chemistry and industry
    • Optimization for Treatment of Contaminated Triethylene Glycol by Electrodialysis Process

      2015, 32(11).

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      Abstract:Abstract: A four chamber electrodialysis was used for purifying the contaminated triethylene glycol solution of Changqing Jingbian Gasfield. The run characteristics such as voltage, running time, flow rate in dilute compartment and inflow concentration of TDS were studied. The optimized process conditions were obtained by using response surface methodology on the based of single-factor tests. Under the optimized conditions of voltage of 48.92 V, running time of 128.09 min, flow rate in dilute compartment of 12.00 L/h, the TDS concentration after treatment could reduce from 1968 mg/L to (38.3±1.2)mg/L. Meanwhile, limited current of electrodialysis processing was determined. When flow rate in dilute compartment reached to 12.00 L/h, the limited current was 0.189 A, and the corresponding limited voltage was nearly 66 V. It was proved that some abnormal phenomena such as concentration polarization were not appeared during the triethylene glycol desalination process.

    • >Oil field chemicals and petroleum additives
    • The Synergistic Effect Between Different Hydrophobically Associating Polymers

      2015, 32(11).

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      Abstract:Abstract: The copolymer (PA) of acrylamide/sodium acrylate/cetyl dimethyl ammonium chloride and the copolymer (PB) of acrylamide/sodium acrylate/sodium 2-acrylamido-tetradecyl sulfonate were blended to form mixed solution (PA/PB system). Fixing the polymer concentration (2000 mg/L) in 5000 mg/L NaCl, based on the apparent viscosity, the optimum compound ratio (3:7) of PA to PB was obtained. At this ratio, the apparent viscosity of PA/PB system was up to 62.7 mPa•s, which was higher than that of PA or PB. Additionally, the effects of NaCl concentration, temperature, shear rate and polymer concentration on the viscosity of mixed system were investigated, which show that the PA/PB system exhibited and there were significant synergistic effects between PA and PB. On the other hand, the characteristic relaxation time (TR) and the platform area modulus (G0) were obtained by rheology measurement to study the synergistic mechanism. The result indicates that the number and structural strength of association structures of mixed system were larger than that of mono-component polymer PA or PB.

    • Preparation and Performance Evaluation of Cross-Linked Polyacrylamide Nanoparticles

      2015, 32(11).

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      Abstract:Using aqueous solution of acrylamide(AM) as the disperse phase, the combination of an oil soluble emulsifier (Span80) with a water soluble emulsifier (Tween80)/kerosene as the continuous phase, the phase diagram of a pseudo-ternary system was made. The inverse microemulsion was prepared according to the best aggregation point of kerosene (52.0wt%), Span80/Tween80(7.8wt%,weight ratio4:1), aqueous phase (40.2wt%) based on the pseudo-ternary phase diagram. Nanoscale polymer microspheres cross-linked with N,N-methylene bisacrylamide(MBA) were synthesized initiated by ammonium persulfate (APS) via the inverse microemulsion polymerization technique at the temperature of 70℃. Effects of the amount of cross-linker agent, initiator and stirring speed on particle size and swelling properties of crosslinked microspheres were investigated using laser diffraction particle size analysis (LPSA). The optimal synthesis conditions were determined as follows: the amount of MBA, APS were 0.60%, 0.50%, the stirring speed was 1000r/min.Swelling behavior of the microspheres obtained under the optimal conditions was discussed. It found that the maximum swelling ratio was 1690, with an absorbency of 17.90g/g in salt solution, the microspheres exhibited fine salt tolerance and high swelling ratio. The microspheres have been characterized by Fourier transform infrared spectroscopy (FT-IR), to confirm the formation of co-polymer. Transmission electron microscopy (TEM) and Scanning electron microscopy (SEM) were adopted to assess the surface morphology of particles prepared. SEM and TEM results demonstrated that polymer microspheres had distinct spherical shape, monodispersity, and uniform distribution of particle size about 200nm. Plugging performance of polymer microspheres latex was studied by the core plugging experiment, the results presented the properties of in-depth profile control step by step of plugging, breakthrough, deepening and plugging again in the cores.

    • >Fine chemical intermediates
    • Improvements on the Synthesis of 6-methoxy-7-ethoxy-4-Chloroquinoline

      2015, 32(11).

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      Abstract:The synthetic methods were studied for 6-methoxy-7-ethoxy-4-chloroquinoline in details. The 2-methoxy-5-nitrophenol was used as the raw material and the title compound was obtained via the O-alkylation, reduction reaction, thermal cyclization, hydrolysis, decarboxylation and chloration. The overall yield was 24%. During the O-alkylation process, compared to the acetone, acetonitrile and DMF, the acetonitrile was proved to be the optimal solvent, which gave rise to the yield increased and the aftertreatment simplified. In addition, one-pot synthesis and without solvent method was bought into the high temperature cyclization process. The one-pot method can greatly simplify the operation and improve the yield. The solvent-free reaction can reduce consumption and pollution. This method can provide an experimental basis for its application with the advantages of simple operation and higher yield from convenient raw materials.

    • Optimization of the Synthesis of 1,3,2-Dioxathiane, 2,2-dioxide

      2015, 32(11):0-0.

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      Abstract:The synthesis of 1,3,2-Dioxathiane 2,2-dioxide was accomplished by 1, 3-propanediol and thionyl chloride as raw materials, potassium periodate as oxidant,using ruthenium(III) chloride as catalyst. The product was characterized by IR and HNMR spectra. The effects of reaction temperature, reaction time, molar ratio of raw material, oxidant species, the amount of catalyst and oxidant on the yield of target product were investigated. The optimal condition was determined as follows: at 40 oC for 60 min, 1,3-propanediol 60 mmol, n(thionyl chloride):n(1,3-propanediol)=1.2:1, m(catalyst):m(1,3-propanediol)=0.0015, m(potassium periodate):m(1,3-propanediol)=0.3:1. The yield of the product could reach 92.75%.