2017, 34(7).
Abstract:The red nano-phosphors, La2(MoO4)3:Eu3+, were synthesized by solvothermal method using lanthanum and europium stearate as starting materials. X-ray diffraction (XRD), transmission electron microscopy (TEM) and fluorescence spectroscopy were employed to characterize the obtained products. The effects of solvent, reaction time, reaction temperature and Eu3+ ions dopant concentration on the morphology and luminescence properties of La2(MoO4)3:Eu3+ were investigated. The results indicate that the tetragonal La2(MoO4)3 :Eu3+ with an average size of less than 100nm were synthesized at 180 ℃ for 12h using isopropyl alcohol as the solvent. The obtained La2(MoO4)3 :Eu3+ can be excited with near-UV 395 nm and blue (462.5 nm) light and exhibit the characteristic red emission of Eu3+ at about 613.5 nm, and the optimal doping concentration is 15 mol %.
GUAN Chun-Long , ZHAO Yuan-Yong
2017, 34(7).
Abstract:Highly pure Cr2AlC powder was synthesized by microwave hybrid heating a Cr/Al/Cr3C2 powder system in the temperature range of 700-1050 ℃ in argon atmosphere. The effect of sintering temperature and constituent on the synthesis of Cr2AlC were studied. By XRD, SEM, DSC, the phase assembly, microstructure and reaction mechanism of samples were analyzed. The results indicated that by microwave hybrid heating,when the molar ratio of mixtures powders 1Cr3C2/2.2Al/1Cr, high pure Cr2AlC powders were obtained at 1050 ℃. When the component Al excess 10at%、20at%、40at%, Cr2AlC with small amount of Cr7C3 were obtained. The amount of Cr2AlC phase was gradually increased by the reaction between Cr-Al intermetallic compounds, un-reacted Cr and Cr3C2 in the temperature range of 700-1000 ℃. And it become a pure phase in the sample with disappearance of intermediate phase at 1050 ℃ for 3min,and the particle size of about 5-8祄.
2017, 34(7):0-0.
Abstract:Novel eco-friendly sulfonated polyurethane/polyacrylate (SPUA) emulsions were synthesized by in situ soap-free emulsion polymerization method using isophorone diisocyanate (IPDI) and sodium sulfonate modified polyester polyol (SDNP) as raw materials and pentaerythritol triacrylate (PETA) with hydroxy and vinyl groups as fictional monomer. The effect of different w(PETA) on properties and morphology of the SPUEA emulsions and films were characterized by dynamic light scattering (DLS),thermo gravimetric analysis (TGA), mechanical properties and atomic force microscope (AFM). The results show that with the w(PETA) increased from 0.5% to 2%, the particle distribution become wider and the particle size increased from 87nm to 112nm, the tensile strength increased from 8.2MPa to 11MPa. With the w(PETA) increased from 1% to 2%, the half decomposition temperature increased from 314.57℃ to 330.57℃. The AFM results demonstrated that the compatibility between the two phased was also enhanced. When the w(PETA) was 2%, the gel content was 84.57%, and water absorption was 8%, the comprehensive performance of the SPUEA film was better. The SPUEA could be used as adhesives. The T-peel strength increased from 6.98N/mm to 11.23N/mm when the PETA mass fraction was up to 2%, and the emulsions could wet the PVC surface well.
2017, 34(7):0-0.
Abstract:The effects of the molecular chain structure, silane content, molecular weight and additives on the tribological properties of the coatings were investigated. The results show that the perfluoropolyether silane coating with CF3 group has good hydrophobicity and hydrophobicity, and the contact angle between water and n-hexadecane is more than 113 ?and 66 ? respectively. High molecular weight, high flexibility molecular chain and higher silane content can improve the abrasion resistance of the coating, and the fluorine-containing alcohol additives can improve the friction stability of the coating. At 1035 g load, the water contact angle of Di-Z-perfluoropolyether silane is over 100?after rub 2500 cycles with steel wool.
2017, 34(7):0-0.
Abstract:A benzimidazole-based fluorescent molecular probe phenyl-1,4-bis [(carbamoylmethyl)-1-pentylbenzimidazole hydrochloride)][M] was synthesized by using p-phenylenediamine, chloroacetyl chloride, benzimidazole and 1-brompentane as raw materials, yield 80.1%. Structure of M was identified by nuclear magnetic resonance spectroscopy and infrared spectroscopy, studying its determination of anions in aqueous solution(HEPES buffer solution, pH=7.4) by fluorescence spectroscopy. The results indicated probe M displayed rapidity, high selectivity, directness for the determination of phosphate inos, the addition of 9.0?0–4 mol/L PO43– in the 1.0?0–5 mol/L M solution led to a 36 nm red-shift in fluorescence maximum, an fluorescence enhancement, and M recognizes phosphate inos without interference from other common anions. All date show that M is a kind of good fluorescence materials.
2017, 34(7):0-0.
Abstract:Modified poly(aspartic acid )/poly(acrylic acid) /carboxymethyl cellulose composite superabsorbent resin was prepared using modified poly (aspartic acid)(KPAsp),acrylic acid (AA) and carboxymethyl cellulose (CMC) as raw materials in an aqueous system. The composition structure, thermal stability and surface morphology of the products were characterized by Fourier-transform infrared spectroscopy(FTIR), thermal gravimetric analysis(TGA) and scanning electron microscopy(SEM).The effects of the amount of CMC and AA on swelling ratio of composite superabsorbent resin were investigated,the results showed that the optimal mass ratio of AA to CMC to modified polysuccinimide (KPSI) was 0.15:3:1,the swelling ratios of prepared composite resin were 830 g/g in distilled water and 130g/g in physiological saline respectively.The salt sensitivity, temperature sensitivity and pH sensitivity of KPAsp / PAA / CMC composite resin with different composition were studied, and swelling properties of resin in artificial blood, artificial urine and different concentrations of ethanol aqueous solution was also studied. The results showed that the salt sensitivity of the composite resin was increased, swelling ratios of resin in different salt solutions were NaCl> FeCl3> CaCl2;The lower critical solution temperature (LCST) of KPAsp/PAA/CMC was 15 ℃ higher than that of KPAsp,the composite resin had the best swelling ratios at pH=5 and pH=9; The maximum swelling ratios of the composite resin were 211 g/g in artificial blood and 142 g/g artificial urine, respectively. The maximum swelling ratios of the composite resin was 295 g / g in the 50% ethanol aqueous solution.
MIN Deng-hao , ZHAO Jia-ping , CHEN Yu-xiang , ZHAO Zhen-dong , CAI Zhao-sheng
2017, 34(7):0-0.
Abstract:β-Caryophyllene- maleic anhydride copolymer (BCPMA) was synthesized by using β-caryophyllene and maleic anhydride as raw material with di-tert-butyl peroxide (DTBP) as initiator and cyclohexanone as solvent.The effects of reaction temperature, reaction time, molar ratio of monomers, the amount of solvent and the amount of initiator on the yield of the copolymer were discussed. The structure of the polymer was characterized by FTIR, 1HNMR, GPC and elemental analysis. Thermal stability of the polymer was determined by thermal gravimetric analysis (TG).The results show that when the conditions of reaction temperature 145℃, reaction time 1h, molar ratio of maleic anhydride to β-caryophyllene 2:1, mass ratio of cyclohexanone to β-caryophyllene 2:1 and initiator dosage 4.5%, the yield of copolymer can reach 92.9%. The initial decomposition temperature of the copolymer is 370.6℃, which indicates that it has high thermal stability.
2017, 34(7):0-0.
Abstract:Objective Superparamagnetic iron oxide nanoparticles modified with oleic acid (O-SPION) was used to prepare the high quality MRI T2 negative contrast agent or magnetic targeting molecular probe load drugs.Our group attempt to use chemical methods different from traditional physical Synthesis methods to prepare O-SPION, and detect the cytotoxicity and permeability for cells in vitro experiment. Methods Preparating superparamagnetic iron oxide nanoparticles with good dispersity and high magnetic response by coprecipitation methods. Modified SPION with oleic acid by condensation reaction after activating the carboxyl of oleic acid. X-ray diffractometry (XRD), Fourier transform infrared (FT-IR) spectra, Laser grain size measure and Transmission electron microscopy (TEM) were used to measure products. Cell viability was determined by MTT assay with human hepatoma cell line HepG2. Prussian blue staining of the O-SPION assayed its ability of cell uptake. Results The average particle size of O-SPIONs was 12 ?1.5 nm. O-SPION had stable chemical structure and lower surface potential. Cell viability demonstrated that O-SPION showed low toxicity or nontoxicity, and its intracellular uptake was greater than the control group.Conclusion Successfully synthesized O-SPION by using chemical methods, and provided experimental basis for preparing high quality MRI contrast agent.
YANG Lan , WANG Chun-hua , LI Chang-peng , LIN Wei
2017, 34(7):0-0.
Abstract:Gelatin nanoparticles (GNPs) of about 100 nm in diameter have been prepared from type B gelatin crosslinked with glutaraldehyde by the modified two-step desolvation process. The effects of the gelatin concentration in dispersions, desolvation solvent (acetone), and the amounts of the cross-linker (glutaraldehyde) have been investigated. The results show that the size and dispersion of the GNPs can be decreased by reducing the content of gelatin in the second dispersed solution before crosslinking. Moreover, the residual acetone in the as-prepared dispersion must be removed completely, since it leads to the forming of larger and less stable particles. Using only 4.5% (w / w gelatin) glutaraldehyde in the 8 g/L (w / v solution) gelatin dispersion can produce stable GNPs with the diameter of 50 ~ 150 nm, a polydispersity index of about 1.4, and Zeta potential < -30 mV. Atomic force microscope (AFM) and transmission electron microscope (TEM) analysis shows that the nanoparticles are spherical morphology and heterogeneous spheres whose edge parts are looser than the cores.
2017, 34(7):0-0.
Abstract:Phenolphthalein-diamine benzoxazine resin (PTBZO) was synthesized using phenolphthalein, diamine and formaldehyde and the corresponding polymer of poly(phenolphthalein-diamine benzoxazine) (PPTBZO) by thermal polymerization was obtained. The chemical structure of PTBZO and PPTBZO was characterized by FT-IR and 1H-NMR. The thermal degradation behavior of PPTBZO was studied with TG-DTG technology and the thermal degradation mechanism was also proposed by the model fitted method and non-model fitted method. At the same time, the dielectric property was also studied. The results show that the fracture of Mannich bond was the major degradation process under the low conversion rate and the introduction of phenolphthalein groups greatly improved the thermal stability of the resin. The thermal degradation reaction mechanism followed the random nucleation and subsequent growth. The complex dielectric constant was 2.65 and 0.05 corresponding to real and imaginary parts, and the dielectric loss tangent ranged from 0.02 to 0.14.
XU Hong-mei , HE Cong-lin , XIA Shi-wen
2017, 34(7).
Abstract:A highly active nitrile hydratase/amidase system was found in Gordonia sihwensis CGMCC 4.2184, which was capable of converting 2-hydroxy-4-methylthiobutanenitrile (HMTBN) to 2-hydroxy-4-methylthiobutanamide (HMTBAm) by nitrile hydratase and then 2-hydroxy-4-methylthiobutanoic acid (HMTBA, methionine hydroxy analogue) followed by amidase in in-situ cascade manner. The effects of substrate concentration, cell concentration, temperature, pH and reaction time on nitrile hydratase and amidase activity were investigated. The thermal stability and pH stability of nitrile hydratase and amidase were determined. The results showed that the optimal reaction conditions were: 50mmol/L HMTBN, 3g/L dry weight cells, 30℃, pH8.0, 30min. Under the optimal reaction conditions, the cells could be used in 23 batches, and the cumulative amount of HMTBA reached 164g/L in 44h, with a yield of 95%.
2017, 34(7).
Abstract:The ethanol extract of Abelmoschus manihot (L.) Medic flowers was separated into four extracts by different polarity solvents sequentially, including petroleum ether extract (PE), ethyl acetate extract (EA), n-Butyl alcohol extract (BA) and aqueous extract (AQ). The protective effects of these four extracts against oxidative injures induced by FeSO4 and H2O2 in mice liver homogenate were investigated by the activities of GSH-Px and ATPase. The four fractions were analyzed by HPLC and DNA protecting activity of the extract with strongest antioxidant capacity was evaluated. The results indicated that at the flavonoids concentration of 300 mg/L, ethyl acetate extract (EA) elevated the activities of GSH-Px by 62.82 U/μg prot in a dose-dependent manner. Aqueous extract (AQ) increased the activities of Na+-K+-ATPase and Ca2+-Mg2+-ATPase by 270.85,232.88 U/μg prot at 300 mg/L and 600 mg/L, respectively. EA was rich in flavonoidsincluding hyperoside (116.19 µg/g ), myricetin (67.70 µg/g ) and quercetin (29.13 µg/g) and was effective in preventing DNA damage dose-dependently. Therefore, the high antioxidant activities of EA may be ascribed to the specific structure and chemical activity of the flavonoids.
2017, 34(7).
Abstract:A series of modified VOx/MSU-1 catalysts were prepared using MSU-1 as the supports, and then were used to catalyze the oxidative dehydrogenation of isobutane to isobutene with CO2. The reaction results showed that the addition of La or Ce could increase the catalytic activity of VOx/MSU-1. La2O3-VOx/MSU-1 was systematically characterized by XRD, H2-TPR and NH3-TPD methods and it was found that the La2O3 addition could improve not only the dispersion of VOx species, active components, over MSU-1 support but also the acid-base properties of catalysts surface, which was favorable to the oxidative dehydrogenation of isobutane. The optimal reaciton conditions were obtained, under which isobutane conversion was 63.6% and isobutene yield was 52.3%. At last, It was demonstrated by the stability experiments of 8 h that La2O3-VOx/MSU-1 possessed higher catalytic stability than VOx/MSU-1.
2017, 34(7).
Abstract:Hexaaquaaluminum methanesulfonate crystals, [Al(H2O)6][CH3SO3]3 were synthesized by hydrothermal reaction of Al(OH)3 with methansulfonic acid. Heating at 265 ℃ for 5 h, (Al2(OH)(CH3SO3)5) was gotten. The six-coordinated enviroment of the central Al atom is also determined by Elemental Analysis, Chemical titration and 27Al MAS NMR measurement. Thermogravimetric and Fourier transform infrared analysis show that the decomposition intermediate product at 265-365 癈 is Al2(OH)(CH3SO3)5 and the final product is amorphous Al2O3 residue with about 0.8 wt% SO3. Tetrahydropyranylation of n-butanol at room temperature in dichloromethane, catalyzed by Al2(OH)(CH3SO3)5 got 100% yielding. After compared, Al2(OH)(MS)5 exhibits the highest catalytic activity (100% yield) among various aluminum salts. Furthermore, Al2(OH)(CH3SO3)5 can be recycled, which enable to be environmentally benign and economical candidates for similar catalytic reactions.
XUE Teng , DU Huang , ZHOU Jian , TANG Erjun , LIU Shaojie , ZHAO Dishun
2017, 34(7):0-0.
Abstract:1-(triethyl four amine) ethyl-3-methyl chloride ionic liquid ([N4MIM]Cl) was prepared on the base of N-methylimidazole by 1,2-dichloroethane to obtain the intermediates 1-chloro-ethyl-3-methyl chloride ionic liquid ([CeMIM]Cl) and then reacting with triethylene tetramine. The chemical structure of [N4MIM]Cl was confirmed by FT-IR and 1HNMR. [N4MIM]Cl possessed a lower REDOX potential through cyclic voltammetry (CV) measurement, E1,2 -0.472V. [N4MIM]Cl presented a perfect coordination property compared with organic ligands. The obtained ionic liquid [N4MIM]Cl coordinated with CuBr was used to catalyze atom transfer radical polymerization (ATRP) of methyl爉ethacrylate (MMA) in 1-allyl-3-methylimidazolium chloride ([AMIM]Cl) and it indicated by gel permeation chromatography (GPC) that the coordination ionic liquid [N4MIM]Cl presented the perfect controllability to the ATRP reactions. The residues of Cu2 in polymerization product polymethyl methacrylate (PMMA) was only 360 mg穔g-1 by atomic absorption spectrometry (AAS) determination. It showed that [N4MIM]Cl was conducive to the separation of catalyst from the obtained product compared with the traditional organic ligands.
LIU Chang-chun , ZHANG Yating , MAO Ruiting
2017, 34(7):0-0.
Abstract:A simple and efficient method was developed for the synthesis of 4-chloro-7-methoxyquinoline-6-carnoxamide as the key intermediate of the anticancer drug Lenvatinib. Using BF3?Et2O as catalyst and solvent, the cascade formylation/addition-cyclization/chloration of 3-methoxyaniline with Vilsmeier reagent and ethyl 3,3-dimethoxypropionate at 90 ℃ for 20 min under microwave irradiation gave 4-chloro-7-methoxyquinoline-6-carboxaldehyde with 72.2% yield. After that, 4-chloro-7-methoxyquinoline-6-carboxamide was synthesized in 84.5% yield via direct oxidative amidation of 4-chloro-7-methoxyquinoline-6-carboxaldehyde with ammonium bicarbonate in the presence of CuI and TBHP under the conditions of CuI 5 mol%, reaction temperature 80 ℃ and reaction time 4 h. The procedure has the advantages of short synthetic route, cheap and easily obtained raw materials, high atomic efficiency, high yield, mild reaction condition, easy operation.
HUA Li , ZHANG Huan , GUO Pei , MA Hongrui
2017, 34(7).
Abstract:ABSTRACT: Characteristics change and differences of polydimethylsiloxane (PDMS) and polymethylvinyl- siloxane (PVMS) membrane before and after extraction were investigated by measuring swelling property and surface performance. The results showed that the swelling degree and the contact angle of PVMS were higher than that of PDMS, indicating excellent hydrophobicity. Chemical structure of membrane changed after treatment. PVMS had better ability of perstraction for organic component than PDMS. Therefore, simple device equipment with PVMS was employed to remove the pentanoic acid from an aqueous solution, and the effects of the influent concentration, influent flow rate, and extraction solvent on permeation extraction were discussed. At the same time, the possible separation mechanism of this process was analyzed. It was found that with the increase of influent concentration, the removal extent and recovery of the pentanoic acid increased but decreased later. The removal extent of PVMS membrane reached 94% at concentration of 7%, and recovery extent reached 45.8% at concentration of 2%. Removal extent with the alkali solution was higher than that with the water in receptor liquor. And receptor liquor with sodium carbonate had better applicability. The removal and recovery extent can be improved by increasing the flow rate between 1 and 20 milliliters per minute, which can enhance separation effect in the practical application.
2017, 34(7).
Abstract:Abstract: In this paper, with P (AAID) as matrix, nano-silica packing under the action of coupling agent, synthesis a new type of organic/inorganic composite drilling fluid loss agent LJ-1.P(AAID) is prepared with monomers IA,AM, AMPS and DMDAAC and the initiator is (NH4)2S2O8 . The optimal molar ratio of monomers is obtained by orthogonal experimental method and the result shows that optimal mass ratio is m(AM):m(AMPS):m(IA):m(DMDAAC)=8:5:1:2. In addition, the optimum reaction conditions as follows: the reaction temperature 65 ℃ and reaction time is 4 h, the initiator adding amount is 1.0 % (based on the mass of monomers). The fluid loss agent LJ-1 chemical structure were characterized by FT-IR and 1HNMR;Finally, evaluated the properties of the fluid loss agent LJ-1.The results showed that the fresh water base fluid loss agent LJ-1 in the pulp quality and quantity was 1.5%, FLAPI=5.8 mL;Salt aqueous fluid loss agent LJ-1 in the pulp quality and quantity of 3.0%, FLHTHP=18.4 mL, LJ-1 has good filtration and salt resistance performance. Additionally, the micro structure of filter cake is conducted by scanning electron microscopy (SEM) and the results shows that the filter cake have a dense grid structure.
2017, 34(7).
Abstract:A series of novel penta-1,4-diene-3-one oxime ester derivatives, which are confirm by IR, NMR, ESI-MS and elemental analysis, were synthesized via the method of combing the oxime esters groups and penta-1,4-diene-3-ones in one molecules. The results of anti-virus bioassays indicated that the curative activity of the title compounds Va against tobacco mosaic virus (TMV) was 61.3%, and the inactivition activity of the title compound Ve against TMV was 91.3%, which were comparable with the commercial agent Ningnanmycin (64.6% and 97.3%, respectively) at 500 μg/mL. Meanwhile, the title compound Vf showed moderate fungicidal activities against G. zeae, F. oxysporum and C. mandshurica at 50 μg/mL, with the inhibition rates reached respectively 48.1%, 56.5% and 66.1%. Furthermore, the title compound Vi exhibited certain insecticidal activity against P. xylostella and A. craccivora at 100 μg/mL, with the inhibition rates reached respectively 61.5% and 42.4%. These bioassys indicates that the penta-1,4-diene-3-one oxime esters has certain antiviral, fungicidal and insecticidal activities, and that some compounds with potent biological activities might be obtained via the structural modification based on the penta-1,4-diene-3-one oxime esters.
2017, 34(7).
Abstract:A series of tyrosine kinase inhibitors which showed antitumor activity were synthesized with 4-chloro-6,7-dimethoxy quinazoline, ethyl 8-bromooctanoate, n-butylbromide and other raw materials, the structuralmodification of N-(3-chloro-4-alkoxyphenyl)quinazolin-4-amine (ARRY-334543) was based on structure-activity relationship of quinazoline derivatives.Structure of these compounds were characterized by NMR and MS , and anti-tumor activity test of the compounds were conducted. Both target compound IX a ~ b posed antitumor activity to MCF-7, BGC-823, A549, DU145 and H1975 cells. Particularly, compound IX a showed the best antitumor activity which 50% concentration inhibition (GI50) is 0.37 μmol/L.