• Volume 34,Issue 8,2017 Table of Contents
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    • >Fine chemical intermediates
    • Facile preparation of acetobromoglucose and acetobromorhamnose

      2017, 34(8).

      Abstract (211) HTML (0) PDF 0.00 Byte (0) Comment (0) Favorites

      Abstract:A facile and efficient one-pot two-step protocol for the preparation of acetobromoglucose and acetobromorhamnose was developed. D-glucose and L-rhamnose were separately treated with HClO4/ Ac2O, followed by addition of AcBr/ MeOH without isolation of the corresponding peracetylated sugars intermediates, which were mono-brominated by HBr generated in situ from AcBr and MeOH. Acetobromoglucose and acetobromorhamnose were obtained in yields of 92.5% and 85.6%, respectively. 2,3,4-Tri-O-acetyl-rhamnopyranose as a by-product during the synthesis of acetobromorhamnose, was recrystallized with dry dichloromethane from the mother liquor of acetobromorhamnose. The above mentioned products and by-product were characterized with 1HNMR, 13CNMR and HRESIMS. This method has distinctive advantages including easy available reagents, convenient experimental procedures and high yields. More importantly, this method could be adapted for industrial production of the titled compounds as well.

    • >Drug and cosmetic materials
    • Preparation and Characterization of Red Light Responsive Cobra Neurotoxin PEG-PLGA Nanocapsule

      2017, 34(8).

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      Abstract:PEG-PLGA was used as the capsule material, and added by photosensitizer pheophorbide to make photo responsive Cobra neurotoxin (CNT) nanocapsule by double emulsion method. The formula was optimized by with encapsulation efficiency, drug loading and particle size as the indexes by single factor tests. Its structure, The thermo rheological properties were analyzed by differential scanning calorimeter, and photo responsiveness were was analyzed by cumulative release. The optimal ratio of PEG-PLGA , CNT and pheophorbide was 40:12.5:1, and the encapsulation efficiency 72.3%±3.6%, drug loading 15.1%±1.3%, average particle size (862±23) nm, and zeta potential (-46.5±3.8) mV were obtained with tight spherical shape and pheophorbide in outer layer of the nanocapsule. Drug release was accelerated under illumination of 650 nm for 30 min with semiconductor laser. This new type of nanocapsule can keep drug stable and sustain release without illumination, but release quickly under red light, thus light controlled targeting can be achieved.

    • >Perfumes and essences
    • Analysis of Aroma Compounds in Coriander by GC-MS and AEDA

      2017, 34(8).

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      Abstract:Volatile compounds of the fresh coriander were analyzed by solvent-assisted flavor evaporation (SAFE) and gas chromatography-mass spectrometry (GC-MS). By NIST 11 Mass Spectral Library searching and retention index comparison, a total of 87 compounds were identified, including 28 hydrocarbons, 20 aldehydes, 22 alcohols, 4 organic acid, 7 esters, 3 ketones, 3 amines and others. GC-O combined with aroma extract dilution analysis(AEDA) was applied to identify aroma active compounds in the fresh coriander , and 21 aroma compounds were identified. 5 chemicals were identified as key aroma compounds (FD≥81), namely trans-2-dodecenal, trans-2-tridecenal, trans-2-tetradecenal, methional and trans-2-decenal.

    • >Functional materials
    • The Synthesis of CO2-Switchable Copolymer and Its Performance Evaluation

      2017, 34(8).

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      Abstract:A copolymer with the performances of being responsive to CO2/N2 simulating, was synthesized by free radical polymerization in aquesous solution, using dimethylamino propyl methyl methacrylamid and acrylamide as the reactive monomers and ammonium persulfate as the initiators. The synthetic conditions with optimum property of CO2/N2 responsiveness were achieved by single factor experiment, which was with the result of molar ratio of AM and DMAPMA being 4:1, mass fraction of monomers being 25%, the dosage of initiator being 0.2% of the total mass of monomers, the ractive temperature being 40癈, the reactive time being 4h. At the first, The structure of the products were characterized by FTIR and 1HNMR. What’s more, The electronic conductivity , Zeta potential and particle size of aqueous copolymer solution on the condition of CO2/N2 were measured, which of the result showed that the products can be highly switchable by CO2/N2 simulating and the process was reversible. A remarkble change of the surface morphology of P(DMAPMA-AM) in aqueous solution between dealing with CO2 and without CO2 were measured. It was showed that the emulsions formed by mixing of diesel and pure water can be emulsification and demusification reversibly on the condition of CO2/N2 when P(DMAPMA-AM) was added to the mixed solution as the emulsifier after carbon dioxide and nitrogen were bubbled through the solution mixed of diesel and water with P(DMAPMA-AM) as the emulsifier.

    • >Surfactants
    • Synthesis and Properties of Lauryl Polyoxyethylene(5) Amine Oxide

      2017, 34(8).

      Abstract (1261) HTML (0) PDF 0.00 Byte (0) Comment (0) Favorites

      Abstract:Lauryl polyoxyethylene(5) amine oxide was synthesized from amine ether and 30% of hydrogen peroxide, the chemical structure of which was confirmed using masss pectral fragmentation and FTIR spectroscopic analysis. The results show that the surfactant has good surface activity, the critical micelle concentration(CMC) is 8.13×10-4 mol/L and γCMC is 35.6 mN/m. In addition, the synthesized surfactant also exhibits stronger emulsifying power and excellent hard water resistance, which is better than raw material AC-1205, the water diversion time is 668s, and the average stability and differential stability in hard water are 5 and , respectively.

    • >Biological engineering
    • Preparation of the Hemoglobin Site-specifically Modified with TEMPO and Study of its Antioxidation

      2017, 34(8).

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      Abstract:4- (N-maleimide)-2,2,6,6-tetramethylpiperidine-1-oxyl (Mal-Tempol) and bovine hemoglobin (Hb) were used as raw materials and the Hemoglobin site-specifically modified on thiol group with nitrogen oxygen free radicals was synthesized. The modification degree of TEMPO was determined by spectrophotometric method. Moreover, the autoxidation of Hb and Mal-Tempol-Hb was discussed with or without the presence of sodium azide (NaN3).The experimental results demonstrated that the autoxidation rate of Mal-Tempol-Hb was much lower than Hb either with or without sodium azide, and the modification effectively improved the antioxidant capacity of Hb.

    • >Modernization technology of traditional Chinese medicines
    • Preparation of 13X Zeolite Film and Its Application for Removal of Lead and Cadmium in Salvia Miltiorrhiza

      2017, 34(8).

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      Abstract:13X zeolite films on α-Al2O3 ceramic tube were prepared by using the method of pre-coating sol, then drying in lower temperature and crystallizing in synthetic solution. The optimal molar composition of synthetic solution was n(Al2O3):n(SiO2):n(Na2O):n(H2O)=1:3.5:7.88:630, and the influences of preparation conditions on formation of 13X zeolite films were investigated. The results showed that continuous and uniform films were observed on α-Al2O3 ceramic tube only with pre-coating sol. It was easier to form continuous films with pre-coating sol than with pre-coating gel. Under the condition that drying temperature and drying time of the pre-coating sol were within 35~45℃ and within 12~18h respectively, continuous 13X zeolite films were easier grown on the surface of ceramic tube judging from XRD patterns and SEM images. By application of the 13X zeolite film to remove lead and cadmium in Salvia miltiorrhiza extract, the removal ratios of lead and cadmium were 86.7% and 44.2% respectively. During the removal process, there was nearly no significant change of active ingredients in Salvia miltiorrhiza extract compared with 13X zeolite particles. The retention rates of solid content, Salvia miltiorrhizanolic Acid B and Rosmarinci Acid were 99.6%, 96.8% and 99.3% respectively. In addition, HPLC fingerprint similarity of Salvia miltiorrhiza extract approached 100% before and after lead and cadmium removing process.

    • >Catalysis,separation and purification technology
    • Sulfonic Acid Functionalized Titanium Oxide Nanotubes as a Solid Acid Catalyst for synthesis of n-butyl levulinate

      2017, 34(8).

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      Abstract:Sulfonic acid functionalized titanium dioxide nanotubes (TNTs-SO3H) was prepared by the reaction of TiO2 nanotubes and (3-mercaptopropyl) trimethoxysilane, then by oxidation of thiols group with hydrogen peroxide. The catalyst was characterized by XRD, FTIR, TEM, TG and Hammett analysis techniques. The catalytic performance of TNTs-SO3H was investigated by the esterification reaction of levulinic acid and n-butyl alcohol. The experiment results revealed that the TNTs-SO3H catalyst exhibited high activity, the n-butyl levulinate yield reached 86.5% under the following conditions: n (levulinic acid): n (n-butyl alcohol) =1:5, w (catalyst) =10%, remperature at 120℃ for 4 h. And the product yield could reach 81.2% when the catalyst is recycled for 7 times.

    • Preparation and Hydrodesulfurization Performance of ZSM-5-MCM-41 Composite Molecular Sieve Supported NiMo Bimetallic Sulfide Catalysts

      2017, 34(8).

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      Abstract:ZSM-5-MCM-41 composite molecular sieve with strong acidity and different Si/Al molar ratios (denoted as ZMC-M(x), M=1.5,2.0 and 2.5 mol/L NaOH respectively, where x represented the SiO2/Al2O3 molar ratios of the mother liquid) were successfully synthesized by assembling zeolite subunits, which generated by hydrolysis of ZSM-5 in a NaOH aqueous solution using cetrimonium bromide as a template. And then MoS2/ZMC and Ni-MoS2/ZMC catalysts were prepared by impregnation method. Different NaOH treatment concentrations were examined to determine the optimum alkali treatment concentration. The effects of Si/Al molar ratio and NiMo bimetallic sulphides on the hydrodesulfurization of thiophene were also investigated using thiophene /n- tetradecane as the model compound. The results showed that with concentration of NaOH increasing the ZMC composite molecular sieve formed more mesoporous phase. However, the high concentration of NaOH treatment destroyed the structure of ZSM-5. Therefore, the optimal NaOH concentration was 2.0 mol /L. With the increase of Si/Al ratio of ZMC, the activity of hydrodesulfurization increases. Moreover, the hydrodesulfurization performance of the composite molecular sieve supported NiMo bimetallic sulfide is better than that of the composite molecular sieve supported MoS2. Under the conditions of H2 pressure of 3 MPa, temperature of 280 ºC and 40 ml (1000 ug/L) thiophene/n-tetradecane, 20%MoS2/ZMC-2.0 (70) and 20%Ni-MoS2/ZMC-2.0 (70) catalysts for the thiophene conversion rate of hydrodesulfurization rate reached 84.1% and 95.2% respectively.

    • The Green Oxidation of Ethyl Lactate to Ethyl Pyruvate over VPO/TiO2 Catalyst

      2017, 34(8).

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      Abstract:Supported vanadium-phosphorus oxide catalysts were prepared from vanadic oxide and phosphoric acid through organic solvent method, and their catalytic performance was investigated in the selective oxidation of ethyl lactate(EL) to ethyl pyruvate(EP). Results showed that the yield of ethyl pyruvate was 73.67% when the VPO catalyst supported by TiO2 with P/V molar ratio 1.40; Under the optimal conditions(n(acetonitrile):n(hydrogen peroxide):n(ethyl lactate)=12:2:1, the amount of VPO/TiO2 catalyst is 10%, 65 °C, 5 h), the conversion of ethyl lactate was 85.24%, and the yield of ethyl pyruvate was up to 80.96%. When the catalyst was reused 5 times, the yield of ethyl pyruvate was still more than 70%. The catalysts were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and determination of average valence state of vanadium, the reaction mechanism is expected to involve a redox cycle in which V4+ in combination with dynamic V5+ sites acts as the active centers.

    • Reaction of ?-oxo Ketenedithioacetals Catalysized by I2 Loaded Montmorillonite

      2017, 34(8).

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      Abstract:Twelve compounds 3,3-bis(ethylthio) acrylophenone and 2-(bis(ethylthio)methylene)-3-oxobutanoate with indole reaction were synthesized by I2 loaded montmorillonite.The stucture of product was characterized by means of infrared spectroscopy(FTIR),nuclearmagnetic resonance spectrum(NMR).The effects of reaction temperature, the amount of catalyst, equivalent ratio of starting materials and reaction time on the reaction were considered.The experiments showed that the optimized reaction conditions were:reaction temperature 80℃, the molar ratio of catalyst MMT/I2 and 3,3-bis(ethylthio) acrylophenone was 0.1:1.0, the molar ratio of 3,3-bis(ethylthio) acrylophenone and indole was 1.0:1.0 and reaction time 1h.The yield of 3-indolyl-3-ethylthio acrylophenone was 89% and still reaches 86% after catalyst recycling for four time.

    • >Perfumes and essences
    • Comparative Analysis of Volatile Flavor Compounds in Douchi Dace by SPME and SDE

      2017, 34(8).

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      Abstract:In order to determine the key flavor compounds of fermented black bean dace and stable product quality,the volatile flavor constituents of Douchi Dace were extracted by solid phase microextraction (SPME) and simultaneous distillation extraction (SDE) and analyzed by gas chromatography mass spectrometry (GC-MS). A total of 113 volatile compounds were identified. A total of 26 compounds were identified by the two extraction methods. According to the results of Gas Chromatography-Olfactometry (GC-O), a total of 9 compounds were regarded as the key aroma components to form the flavor of Douchi Dace and they were 2-pentyl-furan, 2,5-dimethyl-pyrazine, 2-ethyl-pyrazine, 2,3,5-trimethyl-pyrazine, 2-undecenal, anethole, 2-acetylpyrrole, 5-methyl-2-phenyl-2-hexenal and ethyl cinnamate.

    • >Drug and cosmetic materials
    • Synthesis and Anti-cancer Activity of Methacrylic Acid/ Butyl Acrylate grafted onto Bagasse Xylan Gallate

      2017, 34(8).

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      Abstract:Bagasse xylan gallate was synthesized by using bagasse xylan as main raw materials, gallic acid as esterifying agent, triethylamine as activation catalyst and N, N-dimethyl formamide (DMF) as the solvent. The esterification and graft copolymerization of methacrylic acid (MAA)/ butyl acrylate (BA) grafted onto bagasse xylan gallate was carried out by using ammonium persulfate as initiator. The parameters of the process affected on the degree of substitution (DS), grafting rate (G) and grafting efficiency (GE) were investigated. The structure and properties of the product were characterized by FTIR, SEM, XRD and TG-DTG. The results showed that the DS was 0.64 under the conditions of n(bagasse xylan): n(trisacetyl-galloylchloride)=1: 1, m(DMF): m(bagasse xylan)=9.5: 1, the esterification reaction temperature 45 ℃ for 4 h. The grafting rate and grafting efficiency of the product was 23% and 67% under n(bagasse xylan gallate): n(BA/MAA)=1: 2, with the ammonium persulfate dosage being 7% (the total reactant mass), reaction temperature 50℃ for 8 h. The product of anti-cancer activity was evaluated against some tumor cell lines by using a methylthiazolyldiphenyl-tetrazolium bromide (MTT) method. The results showed that the inhibition rate on cancer cells of the liver reached to 28.83%.

    • >Food and feedstuff chemicals
    • Preparation and Structure Characterization of Chitosan - Gelatin Composite Membrane Modified by Walnut Green Husk Polyphenol

      2017, 34(8).

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      Abstract:A series of chitosan-gelatin modified by walnut green husk polyphenols with different ratios of chitosan to gelation were prepared,and the mechanical properties, solubility,water vapor permeability (WVP) and DPPH free radical clearance of the modified composite membranes were investigated. The structure and compatibility of the modified composite membranes were analyzed by X-ray diffraction(XRD),infrared spectroscopy (IR)and Scanning Electron Microscope (SEM).The results show that the comprehensive performance of modified composite membrane is the best when the dosage of polyphenols is 2% and the ratio of chitosan to gelatin is 45:55. The tensile strength, solubility, WVP, DPPH free radicals clearance of the modified composite membrane respectivily are 49.8 MPa, 16.5% ,0.15 (g. m.)/(h.m2. kPa) and 80.40%. The crosslinking of polyphenols with chitosan and gelatin and the compact structure also with the good compatibility of the modified composite membrane are indicated by XRD,IR and SEM. The research illustrates that walnut green husk polyphenols can improve the internal structure and promote the comprehensive performance of the modified composite membrane.

    • >Electro-organic chemistry and industry
    • Effect of Alumina/polyvinyl alcohol Layers on Performance of Polypropylene Separators

      2017, 34(8).

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      Abstract:In order to improve the electrolyte wettability and thermal stability of polypropylene separator, an Al2O3-coated composite polypropylene separator was prepared with Al2O3 as ceramic particle, polyvinyl alcohol as binder and燿eionized爓ater as solvent through a direct coating process. The bare pp separator and coated pp separator were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM), contact angle testing, elecrolyte wettability and thermal resistance testing. It was found that with the Al2O3/PVA layer, the electrolyte uptake of the coated separator increased from 98% to 203%, and the thermal shrinkage in 170℃ for 1 h decreased from 46.1% to 24.4%. Moreover, compared to bare PP separator, the coated PP separator exhibited better discharge C-rate capability and cycling performance when investigated in Lithium-ion Batteries.

    • >Rubber and plastics auxiliaries
    • Synthesis and Application of Flame Retardant Dihydroxy Silicate Disulfide PEPA Ester

      2017, 34(8).

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      Abstract:A dihydroxysilicate disulfide PEPA ester flame retardant, dihydroxy silicate bis-1-thiophospha -2,6,7- trioxabicyclo [2.2.2] octyl-4-methyl ester(SDSPE), was synthesized by silicon tetrachloride(STC) and 1-thiophospha-4-hydroxymethyl-2,6,7-trioxabicyclo [2.2.2] octane (SPEPA). The effects of solvent, reaction temperature, reaction time and mass ratio on the yield were investigated. The optimal conditions were selected as follows: dioxane as solvent, the first step kept the reaction going at 30℃for 6h when the molar ratio of STC and SPEPA was 1:2.1, and then reacted with two times amount of water at 60癈 for 4h to obtain a dihydroxysilicate disulfide PEPA ester. The yield could reach to 93.9%. The structure and flame retardance of the product were characterized by means of FTIR, 1H -NMR, TG-DTA analysis and LOI technique. Results showed that the product had a good thermal stability and high flame-retardant efficiency when applied to 191 unsaturated polyester.

    • >Papermaking chemicals
    • Preparation of Carboxymethyl Chitin Based Retention and Drainage Aids and Their Retention and Drainage Behaviors Investigation

      2017, 34(8).

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      Abstract:A type of novel retention and drainage aids, water-soluble carboxymethyl chitin (CCH) with different degree of substitution (DS=0.4, 0.5, 0.6), were prepared using chitin (CH) as the raw material and sodium chloroacetate as etherifying agent. The structure of CCH was characterized by infrared spectroscopy (IR), x-ray diffraction analysis (XRD). The results indicated that carboxymethyl group was successful introduced into CH, which resulted in a destruction of crystalline region of CH. The retention and drainage tests showed that the retention and drainage performances became better with the increasing of DS, and the best performances were obtained when the addition amount of CCH with DS=0.6 was 0.5%. In order to further improve the retention and drainage performances of CCH, CCH/PAC dual system was developed by introducing polymeric aluminum chloride (PAC) with high cationic charge density, the retention and drainage performances of CCH/PAC were significantly better than alone using CCH.

    • >Acrylic series chemicals
    • Preparation and Properties of Waterborne nitrocellulose Emulsion Modified by Fluoroacrylate

      2017, 34(8).

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      Abstract:With nitrocellulose(NC),isophorone diisocyanate(IPDI),acrylic acid(AA),hydroxyethyl methacrylate(HEMA),perfluoroalkyl ethyl acrylates(FA) and triethylamin(TEA) as main raw materials,the waterborne nitrocellulose emulsion modified by fluoroacrylate(WNC) were prepared by self emulsification.structure and properties of emulsion and thin film were characterized by FTIR,TEM,nano particle size analyzer,dynamic rheometer and contact angle analizer,the effects of monomer polymerization temperature,the n(AA):n(HEMA) and the amount of fluoroacrylate on the properties of emulsion and thin film were also studied.The results show that the WNC emulsion showed a stable performance and the particles of emulsion were regularly spherical with a core-shell structure.When the monomer polymerization temperature was 60℃,the n(AA):n (HEMA) was 3:1 and the mass fraction of fluoroacrylate was 1%, the particle size of WNC emulsion was smaller with narrow particle size distribution.The average particle size and polydispersity index(PDI) were 54nm and 0.042, respectively.Compared with WNC films unmodified,the water absorption of the modified WNC films was reduced to 2.0% and contact angle was increased to 120 °,which exhibited the modified WNC film has excellent water resistance.

    • >Other
    • Keratin Was Extracted from Rabbit Hair Using L-cystein as Reductive Agent

      2017, 34(8):0-0.

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      Abstract:Keratin was extracted from rabbit hair using L-cystein as reductive agent under the condition which is pH=10.5,L-cystein 0.165 mol/L,urea 8mol/L,reaction time 5h,reaction temperature 75℃. The results of the experiments presented the dissolution rate of rabbit hair was 74.12%,the recovery rate of final keratin after disdialysis and freeze drying of dissolved solution was 69.23%,in which the mass fraction of keratin was as high as 99.38%. The molecular weight of rabbit hair keratin mainly concentrated in about 11 kDa via polyacrylamide electrophoresis SDS-PAGE.The internal structure of Keratin was characterized by infrared spectrum (FTIR), Raman spectroscopy,X-ray diffraction (XRD) and differential scanning calorimetry (DSC). From the result,with the process of rabbit hair dissolution,about 35% (in mole fraction)disulfide bond in the rabbit hair was destoried by L-cystein,which resulted in the change of keratin secondary structure in which the content of α-helix structure decreased,and the content of β-sheet increased.