WU Wang-bo , ZHANG Gui-ju , WANG Rui , XU Bao-cai
2016, 33(8).
Abstract:Novozyme 435 was employed as biocatalyst for the transesterification of methyl laurate and glycerol in t-butanol producing glycerol monolaurate (GML). Emzymatic synthesis process was optimized by single-factor and orthogonal experiment using the content of glycerol monolaurate in the reaction system as the index. The results show that the optimum conditions were as follows: substrate molar ratio 1:5,substrate concentration 20%,reaction temperature 55 ℃,enzyme amount 7%,water content 20%,rotation rate 100 r/min,and reaction time 1 h. The content of glycerol monolaurate in the reaction system was 71.86% under the optimal synthesis conditions,After the recycle of unreacted methyl laurate,After purification the content of glycerol monolaurate in the final product was higher than 95%,with the maximum content 98.76%,while the content of glycerol dilaurate (GDL) was no more than 5%. Under the optimal conditions, the content of glycerol monolaurate decreased to 68.36% after being reused for six times, which was 71.75% in the first test.
WANG Xin-ying , HUANG Hong-xia , XIE Wen-qiang , YU Wen-wan , KONG Xiang-fei
2016, 33(8).
Abstract:In order to improve the electrochemical properties of La-Mg-Ni system hydrogen storage alloy, graphene was synthesized and added into the hydrogen storage alloy La0.73Ce0.18Mg0.09Ni3.20Al0.21Mn0.10Co0.60. It was found that the alloy still retained the phase structure. Electrochemical studies showed that the maximum discharge capacity of these electrodes decreased slightly. After adding 1%, 2% and 5% grapheme, the cyclic capacity retention rate after 50 charge-discharge cycles was significantly enhanced from 63% of original alloy to 75%, 78% and 73%. As the graphene content was 2%, the high rate dischargeability (HRD) at the discharge current density of 900 mA/g increased from 79.8% to 83.9%, and the exchange current density I0 and the limiting current density IL improved from original 54 mA/g and 512 mA/g to 281 mA/g and 1537 mA/g, respectively. Furthermore, the addition of graphene had a positive effect on the anti-corrosion capability of electrodes.
2016, 33(8).
Abstract:The effect of fluorination treatment on La0.94Mg0.06Ni3.49Co0.73Mn0.12Al0.20 hydrogen storage alloy was studied to improve its electrical chemical properties. The results of X-ray diffraction(XRD) and Scanning electron microscope(SEM) showed that the phase composition of the alloy were changed after fluorination treatment, there is a new phase that is MgF2; some particles of MgF2 were formed on the surface of the alloy, When the concentration of NH4F was 0.3 mol/L, the maximum discharge capacity Cmax of the alloy electrode increased from 346.4 mAh/g to 378.0 mAh/g, the capacity retention rate S50 was improved from 69.5% to 74.3%, the exchange current density was improved from 122.3 mA/g to 188.5 mA/g, the limiting current density was improved from 891.7 mA/g to 1162.1 mA/g, the corrosion potential was improved from -0.895V to -0.849V, electrochemical reaction impedance was reduced.
2016, 33(8).
Abstract:Carboxymethyl chitosan(CMC) was prepared by reacting of chitosan with chloroacetic acid. The structure of CMC was characterized by Fourier transform infrared spectrum (FTIR), nuclear magnetic resonance spectrum (1HNMR), environmental scanning electron microscope (ESEM) and X-ray diffraction (XRD). In addition, the effects of chloroacetic acid dosage, lye concentration, alkalization time, and reaction temperature on the O-substitution degree (O-DS,Y1) and N-substitution degree(N-DS,Y2) were investigated. Furthermore, on the basis of single factor experiment, the corresponding technological parameters were optimized by using the BBD mathematical model in Box-Behnken experimental principle of response surface methodology (RSM). It was found that that the optimal processing for the preparation of carboxymethyl chitosan were as follows: chloroacetic acid dosage 5.71 g, lye concentration(NaOH) content 54%, alkalization time 7h, and the reaction temperature 40℃. The products has highest DS, Y1=72.13%,Y2=28.57%. In comparison with predictive results of the regression model, the relative error is only 0.22% and 0.26%. respectively.
Zhang Zhengdong , Li Yang , Wang Futao , Pan Yuanfeng
2016, 33(8).
Abstract:Cationic polymer latex, poly(styrene/butyl acrylate-co- glycidyl methacrylate) [P(St/BA-co-GMA)], with core–shell structure was synthesized by a two-step semi-batch emulsion polymerization with styrene (St), butyl acrylate (BA) and glycidyl methacrylate (GMA) as monomers, cetyl trimethyl ammonium chloride (CTAC) as cationic surfactant, ethylene glycol dimethacrylate (EGDMA) as crosslinking agent, 2,2'-azobis(2-methylpropionamidine) dihydrochloride (AIBA) as cationic initiator. The influence of surfactant dosage, initiator dosage, reaction temperature and time on the properties of latex were investigated. The monomer conversion of cationic latex reached 98.03% when the reaction proceeded under the following conditions: surfactant dosage of 6 %, initiator dosage of 0.5%, and 2 h reaction time at 80 ℃. The mean particle size and zeta potential of the resulted latex particles were 57.21 nm and +47.62 mV, respectively. The core-shell structure of latex was confirmed by Transmission Electron Microscope (TEM) and laser particle size analyzer. The latex was applied for hydrophobic modification of bagasse fibers. The water contact angle of the modified fiber was increased from 0°to 98°, compared with the untreated fiber, which indicated that the modified bagasse fibers were rendered hydrophobic by the cationic latex nanoparticles.
GONG Jian-bo , HUANG Yan , ZHONG Cong , ZHANG Qi , HUA Ming-qing , ZHANG Xiao-yan , WU Jing-bo
2016, 33(8).
Abstract:Fe3O4@BSA nanoparticles (NPs) were successfully synthesized, and bovine serum albumin (BSA) coating upon the surface of Fe3O4 NPs played the role of stabilizer and disperser. The prepared Fe3O4@BSA NPs were characterized and analyzed by Fourier transform infrared spectra (FTIR), X-ray diffraction (XRD), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). The results suggested the successful synthesis of Fe3O4@BSA NPs. The content of BSA was about 18.9 % in Fe3O4@BSA NPs. The results of MR imaging in vivo showed that the T2 MRI signals were improved gradually with increased iron concentrations, which presented an obvious negative MRI effect of Fe3O4@BSA NPs. The transverse relaxivity (r2) of the Fe3O4@BSA NPs was evaluated as 148.18 L/(mmol·s) at 0.5 T. These preliminary studies indicated that the obtained Fe3O4@BSA NPs could be used as promising T2 contrast agents for magnetic resonance imaging.
2016, 33(8).
Abstract:Tung oil anhydride(TM) was synthesized through a Diels-Alder reaction with tung oil(TO) and maleic anhydride(MA) as raw materials.Tung oil-based waterborne UV-curing resin was prepared via neutralizing and hydrating after tung oil anhydride(TM) reacting with hydroxyl ethyl acrylate(HEA). The molecular structure of synthetic product was characterized through the infrared spectra (FTIR) and nuclear magnetic resonance hydrogen spectrum (1H NMR) .The ratio of tung oil(TO), maleic anhydride(MA), hydroxy ethyl acrylate(HEA) and triethylamine(TEA) was considered to be influence on emulsion properties,curing properties and curing film performance of tung oil-based waterborne uv-curing resin.The results showed that the best mole ratio of raw materials was 1:2.5:2.5:2.5. Under this ratio, the emulsion stability,light curing activity and curing film performance are the most excellent.
2016, 33(8).
Abstract:In the present study, a novel Zr-pillared montmorillonite(Zr-MMT) macroporous materials (P-ZMt) was developed by dry pressing molding combining with pore forming agent. The structure and morphologies of P-ZMt was characterized by X-ray diffraction(XRD), scanning electron microscope(SEM), the thermal properties of samples were studied by thermal gravimetric analysis (TG), and the porosity of P-ZMt was detected by mercury porosimetry analyzer. The influence of porosity, permeability coefficient and specific surface area(SSA) including the mass ratio of different pore forming agent, pore forming agent dosage, pressure on of P-ZMt were evaluated. The adsorption of Cu2+, Cr3+, Pb2+, Cr6+ on P-ZMt was discussed. The optimum conditions for forming P-ZMt were: m(PMMA):m(AC)= 1:2, w(pore forming agent)=40%, pressure and calcination temperature were 20MPa and 550C, respectively. The pore size of P-ZMt varied from around 150μm to 250μm and the porosity up to 39.85%. The macropore of P-ZMt were interpenetration and the hole wall rendering three-dimensional honeycomb pore. When the adsorbent dosage was 1g/L, the removal rates of P-ZMt for Cr3+, Cu2+, Pb2+ were over 90%, while for Cr6+ almost no adsorption.
2016, 33(8).
Abstract:The pertraction effect of monocarboxylic acids by methyl silicone rubber (PDMS) and vinyl silicone rubber membrane (PVMS) were investigated. Relations between the organic structure parameters and pertraction effect were founded. The pertraction experiment demonstrated that PVMS membrane have good extraction effect on formic acid and acetic acid compared with PDMS membrane. The pertraction effect of monocarboxylic acids were analyzed by organic structure parameters and silicone rubber membrane structure. Results showed that with the increase of octanol-water partition coefficient (Kow or P), molecular molar volume (Vm) and molecular polarizability (a) that extraction rate of monocarboxylic acids increased; however, extraction rate decreased with the increase of mass intrinsic solubility(S). Pertraction experiments showed a significant correlation between extraction rate and log P(R2 was more than 0.96), as well as a correlation between extraction rate and Vm (R2 was more than 0.81). Dipole moment (u) does not have apparent regularity in this study.
CHEN Xing , GUO Rui-wei , YUAN Cheng , ZHANG Jian-hua
2016, 33(8).
Abstract:A new hydrolysable crosslinking agent LC with β-quaternary ammonium structure was synthesized by quaternization reaction of dimethylaminoethyl acrylate and 1,4-dibromobutane. By inverse miniemulsion polymerization, a series of cross-linked polyacrylamide (PAM) microspheres with delayed-swelling characteristics were prepared, containing LC alone or LC and N, N-methylene bisacrylamide (Bis). The particle size of the microspheres was 300 nm ~ 500nm, and the distribution was narrow. The delayed-swelling characteristics of crosslinked PAM microspheres can be dissected by light transmittance. The research showed LC showed faster hydrolysis rate than non ionic acrylate. The swelling time (tS) was 2 d as pH=8.9, while tS was increased to 40 d. Its hydrolysis rate was decreased with the decrease of pH, and the weak acid condition can inhibit the hydrolysis of LC. The swelling time can be adjusted by the usages of LC (2 % ~ 5 %)and Bis(0 ~ 0.05 %), the temperature(75 ~ 100 ℃) and pH(5.0 ~ 8.9), and changed from 2 d to 40 d. The new hydrolysable cross-linker LC and the PAM microspheres prepared by LC-Bis compositecross-linkers have application prospects in depth profile control and water plugging.
2016, 33(8).
Abstract:The seepage experiment of the hydrophobic association polymer was carried out in the two stage series flat sand inclusion seepage model. The results showed that the hydrophobic association polymer in the two stage series possessed three different types of seepage characteristic in the porous media and associated with the permeability of the porous media; The first seepage type (I) was that the polymer had the same drag coefficient on the direction of flow when the permeability was greater than 1.8 μm2. The second seepage type (II) was that the polymer had an increase of the drag coefficient on the direction of flow when the permeability was equal to 1.8 μm2. The third seepage type (III) was that the polymer had a decrease of the drag coefficient on the direction of flow when the permeability was less than 1.8μm2. By comparison of the experimental results of single stage and two stage series plate clamp flow experiment of sand flow models, it was proved that the drag coefficient difference of the second seepage type and the third seepage type was resulted from the changes in the seepage aggregate. The seepage aggregate size changes were studied through the single-stage and two-stage tandem microporous membrane filtration experiment and dynamic light scattering experiment. The results showed that and the difference of the drag coefficient of the above mentioned two seepage types was caused by the size change of the hydrophobic association polymer in the series plate clip sand model.
CHEN Ze-yang , HU Xue-yi , FANG Yun , ZOU Mengyao
2016, 33(8).
Abstract:Isotridecanol polyoxyethylene-7 ether (E1307) was synthesized by CH3OK catalyzed ethoxylation of iso-tridecanol and ethylene oxide in order to improve the qualities of the products with a broad polydispersity to replace the product with a narrow polydispersity. The effect of the reaction parameters on the product quality, especially the lowest transparent temperature and wetting power, were well investigated, and the experimental results showed that the moisture and the catalyst dosage were the two main influence factors. Moisture was removed as far as possible from isotridecanol under vacuum at 100 oC for 1 h, and then the ethoxylation was catalyzed by CH3OK (0.3%wt) at 120 oC and 0.3 MPa EO, and the product of E1307 was obtained with the lowest transparent temperature of 10 oC and wetting power of 163 s which is superior to the commercial product with a narrow polydispersity.
LAI Xiaojuan , SONG Peiyan , WANG Lei , YU Lili
2016, 33(8).
Abstract:Waterborne polyurethane/polyacrylate emulsion (WPUA) was synthesized with poly-caprolaclone glycol (PCL), isophorone diisocyanate (IPDI), 2,2-dimethylol butyric acid (DMBA), methyl methacrylate (MMA) and butyl acrylate (BA). Glycidyl methacrylate (GMA) and allyloxy hydroxyl propanesulfonic salt (AHPS) were introduced to the waterborne polyurethane/polyacrylate system and a stable epoxy-modified waterborne polyurethane/polyacrylate (EPUAS) composite emulsion had been obtained. The structure, morphology and properties of polyurethane/polyacrylate emulsion and films were characterized by fourier transform infrared spectroscopy (FTIR), transmission electron microscopic (TEM),X-ray diffraction analysis (XRD) and thermogravimetric analysis (TGA). The amount of GMA on properties of the polyurethane/polyacrylate emulsion and films were discussed. The results showed that EPUAS emulsion shows a core - shell structure, with the increase of w (GMA) from 1 % to 4 %, the thermal stability of the film were improved, the tensile strength gradually increased from 6.8 to 12.3 MPa, elongation at break reduced from 12.2 % to 6.6 %, the degree of crosslinking increased from 60.1 % to 81.7 %, the particle size of the emulsion waw increased from 198 nm to 273 nm, and with the w (GMA) at 4 %, the water absorption, solvent absorption rate of EPUAS film each was fallen to 7.2 %, 16.3 % , whose overall performance achieved the best.
LI Jiang-nan , Wang Zhan-wei , Tang Sheng-biao , Li Jin-ling , Li Ming , Jiang Shen-de
2016, 33(8).
Abstract:the paper reports an efficient method to prepare octacosanol. It started from the economical chemical erucic acid. The route went through acylation, Dieckmann ring-opening, hydrogenation, Wolff-Kishner reduction and LiAlH4 reduction to give octacosanol with 99% purity. This synthetic process contains 6 linear steps with 65.4% overall yield. Furthermore, this method was utilized for 50 kg scale manufacture successfully. The main advantage of the method includes economical and easy availability of starting materials, relatively safe and simple operation, repeatable overall yield and simple purification process for intermediates and final products.
2016, 33(8).
Abstract:This work indicates that the nitration of guanidine salt can be carried out in continuous mode using the microreactor system. With sulfuric acid guanidine as raw material and sulfuric acid and sulfuric acid mixture as nitrating agent,the influences of the mixed acid concentration, reaction temperature, residence time, ratio of two materials on the yield of nitroguanidine were carried out. The optimal reaction conditions are shown as follows: 90% HNO3: 98% H2SO4 = 2: 1 (v / v), 1:1. 2 of molar ratio of sulfuric acid guanidine and nitrating agent. The conversion of the sulfuric acid guanidine can reach 87.9% and the yield of the nitroguanidine can reach 86.1%. Compared with the traditional process, new technology based on micro-channel continuous flow greatly improves production efficiency and reduces costs.
LUO Nian-hua , ZHENG Da-gui , ZHOU An-xi , WANG Yong , LIU Wen-jie , YOU Chong-ren
2016, 33(8).
Abstract:A series of cinnamyl morpholine(2a~2i)were synthsized by the chlorination of substituted cinnamic acids(1a~1i)with thionyl chloride in DMAc at 0 ℃ for 20 min,followed by amidation in situ with morpholine at 25 ℃ for 7 h. The yield of 2a~2i were 81.6%~95.4%. The structures were characterized by 1H NMR、13C NMR、IR and MS. The proposed mechanism for the promotion of dimethylacetamid on the syntehsis was suggested.
ZHANG De-qi , Tariq Aziz , FAN Hong
2016, 33(8).
Abstract:Fluorine contained polysiloxanes exhibit the advantages of both fluorine and silicone, such as excellent thermal resistance, lubricity, and surface property. They are widely applied in many fields, such as petrochemicals, textile, machinery, etc. This paper reviews the preparation of fluorine contained polysiloxanes, such as hydrosilylation, hydrolysis and ring-opening polymerization. The relationship between their molecular structure and properties are discussed, such as interaction mechanism of fluorine contained silicone oil with different material interfaces and the corrdination effect of fluorine and silicone. Their applications as lubricants, antifoaming agents, finishing agents, and super hydrophobic materials are also introduced. Through molecular chain structure modification, as well as adding suitable additives (such as organophosphine and ferrous-organic compounds), the surface properties of fluorine contained polysiloxanes, including anti-oxidation stability and anti-wear properties are hopefully to be largely enhanced.
2016, 33(8).
Abstract:Sequential extraction method was used to separate the ethanol extract of Abelmoschus manihot (L.) Medic flowers. Four extracts were obtained by different polarity solvents, including petroleum ether, ethyl acetate, n-Butyl and water. The antioxidant properties of the four fractions were evaluated by the reducing power and scavenging activities of three free radicals, namely hydroxyl radical (•OH), superoxide radical (O2-•) and DPPH radical (DPPH•). The extract with strongest antioxidant capacity was investigated by measuring the effects on hemolysis of mice red blood cells, malondialdehyde (MDA) generation in mice liver homogenate and mitochondria and the swelling degree of liver mitochondria. The order of radicals scavenging capacity of the four extracts was found to be DPPH•>•OH>O2-•and the ethyl acetate extract (EA) showed the highest radicals scavenging capacity. The EC50 of these free radicals were 3.52,44.96,376.87 μg/mL, respectively. The effect of EA on anti-lipid peroxidation were studied by in vitro system. EA could inhibit the hemolysis of mice red blood cells significantly (p<0.05) , reduced the generation of MDA in mice liver homogenate and mitochondria in the concentration range of 50~500 μg/mL and alleviated the swelling of liver mitochondria in a dose-dependent manner.
2016, 33(8).
Abstract:Using commercial MoS2 as raw material, the exfoliated MoS2 catalyst with a large specific surface area was prepared by adopting n-butyl lithium embedded into the MoS2 crystals. BET, XRD, SEM characterization results showed that the improved preparation method via adding cationic surfactant CTAB into the exfoliation process could reduce the height of the stack layers of MoS2, whereas for the adding of anionic surfactant, the exfoliation effect could not be promoted. The main products for the hydrodeoxygenation of p-cresol by MoS2 catalyst were 4-methylcyclohexene, methylcyclohexane and toluene. The exfoliated MoS2 catalyst had two catalysis activated sites which located at the “Edge” and the “Rim” of the layers of the crstals and [基金项目:国家自然科学基金(No. 21306159, 21376202) *联系作者:杨运泉(1963-),男,教授,博导,Tel:13055142055,E-mail:yangyunquan@xtu.edu.cn 作者简介: 杨司军(1990-), 男, 湖南省怀化市人, 硕士研究生, 主要从事催化过程及催化新材料研究。 Tel: 15773206350, E-mail:Yangsj900327@163.com]the HDO reaction was much easier to occur at the "Edge". Adding Ni or Co into the exfoliation MoS2 catalyst could improve the activity of HDO and the introduction of Ni could promote the toluene converting into methylcyclohexane, implying that the addition of Ni into the exfoliation MoS2 is more beneficial to the improvement of the fuel oil quality origined from bio-oil raw material. However, the HDO reaction activity of the exfoliated MoS2 was not yet high enough with the addition of Ni or Co into the catalyst, this may be ascribed to the limitation of the specific structure and the chemical activity of MoS2.
ZHONG Sheng-hui , XU Shi-hai , BAI De-fa , CHEN Jian-wei , NIE Wei-heng
2016, 33(8).
Abstract:With N-[(9H-Fluoren-9-ylmethoxy)carbonyl]-leucine ( Fmoc-Leu-OH ) and N-[(9H-Fluoren-9-ylmethoxy)carbonyl]-proline ( Fmoc-Pro-OH ) as starting materials, the classic Fmoc solid phase synthesis scheme for cyclopentapetide was employed. The linear peptapeptides were synthesized by protecting and deprotecting the amine using standard Fmoc solid phase peptide synthesis, including N-methylated amino acid. The cyclization step was completed using Benzotriazol-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate ( PyBOP ) as coupling reagent. Herein, two Galaxamide analogues G1 and G2 were synthesized and characterized by means of 1HNMR, 13CNMR, ESI-MS. Their anti-tumor activity in vitro were investigated through the MTT assay. The results demonstrated that proline-containing Galaxamide analogue G2 possess potent cytotoxicity on human breast cancer cell line MCF-7, which exhibited IC50 values of 5.85 mg /L.