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Table of Content

    10 July 2014, Volume 35 Issue 7
    Content
    Cover and Content of Chemical Journal of Chinese Universities Vol.35 No.7(2014)
    2014, 35(7):  0-0. 
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    Articles: Inorganic Chemistry
    Synthesis and Crystallization Process of Polymorph A Enriched Beta Zeolite in the Presence of Two New Quaternary Ammonium Bases
    GUO Wen, YAN Wenfu, XU Ruren, WANG Yongrui, MU Xuhong
    2014, 35(7):  1363-1368.  doi:10.7503/cjcu20140340
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    In the presence of trimethyl-cyclohexyl ammonium hydroxide or ethyl-dimethyl-cyclohexyl ammo-nium hydroxide, chiral polymorph A enriched Beta zeolites were synthesized. The products were further cha-racterized by X-ray powder diffraction(XRD), scanning electron microscope(SEM), 29Si magic-angle spinning nuclear magnetic resonance(29Si MAS NMR) and nitrogen adsorption-desorption analyses. The crystallization process of the polymorph A enriched Beta zeolite in the presence of trimethyl-cyclohexyl ammonium hydroxide and the influence of the water content in the initial mixture on the enrichment of the polymorph A were investigated. The results showed that the appropriate water content in the initial mixture was critical for the formation of polymorph A enriched Beta zeolite, the enrichment of chiral polymorph A occurred in the early stage of crystallization and the degree of the enrichment of polymorph A did not change during the crystallization.

    Extraction of Eu(Ⅲ) and Am(Ⅲ) from Nitric Acid Solution with Bisdiglycolamides
    HUANG Song, DING Songdong, JIN Yongdong, MA Lijian, XIA Chuanqin, LI Shoujian, WU Yuxuan, HUANG Huang
    2014, 35(7):  1369-1378.  doi:10.7503/cjcu20140198
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    Two bisdiglycolamides, N,N,N''',N'''-tetraoctyl-N',N″- ethanediyl bisdiglycolamide(TOE-BisDGA) and N,N,N''',N'''-tetraoctyl-N',N″-m-xylylene bisdiglycolamide(TOX-BisDGA), were synthesized by a mixed anhydrides method. Their extraction behaviors of Eu(Ⅲ) and Am(Ⅲ), as well as the extraction of nitric acid were investigated from nitric acid solution using kerosene/n-octanol(volume ratio 90∶10) as diluent. Nitric acid was extracted as the form of HNO3·BisDGAs by BisDGAs at less than 1.0 mol/L HNO3. The distribution ratios of Eu(Ⅲ) and Am(Ⅲ) increased with the increase of nitric acid concentration. TOE-BisDGA had a stronger extraction power for Eu(Ⅲ) and Am(Ⅲ) than TOX-BisDGA. Slope analyses showed that Eu(Ⅲ) and Am(Ⅲ) were extracted as di-solvated species by BisDGAs. The distribution ratios of Eu(Ⅲ) and Am(Ⅲ) decreased with temperature rise, which suggested that the extraction reaction of Eu(Ⅲ) and Am(Ⅲ) is exothermic. The two BisDGAs displayed a higher affinity toward Eu(Ⅲ) than Am(Ⅲ). In the mean time, the extraction mechanism was described and the apparent extraction equilibrium constant as well as Gibbs free energy change, enthalpy change and entropy change were presented. In addition, their Eu(Ⅲ) complexes were analyzed by IR and UV spectra.

    In-situ Preparation and Microwave Absorption Performances of Fe-Ni/C Composite Nanofibers
    XIANG Jun, ZHANG Xionghui, YE Qin, LI Jiale, SHEN Xiangqian
    2014, 35(7):  1379-1387.  doi:10.7503/cjcu20131212
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    Fe-Ni/C composite nanofibers with an average diameter of about 215 nm were fabricated via an in-situ decomposition and reduction of electrospun polyacrylonitrile/iron acetylacetonate/nickel acetylacetonate precursor fibers during the thermal stabilization and carborization processes. The Fe-Ni alloy nanoparticles in-situ generated during carbonization are well distributed on the surface and inside the nanofibers and encapsulated mostly by the ordered graphitic layers, which can avoid the direct exposure of Fe-Ni alloy phase to air and preserve the structural and interfacial stabilization of Fe-Ni alloy nanoparticles. By dispersing the Fe-Ni/C composite nanofibers homogeneously into a silicone rubber matrix, their electromagnetic parameters were measured in the frequency range of 2—18 GHz and the influences of carbonization temperatures on the electromagnetic characteristics and microwave absorption properties were investigated. It is found that the absorbing coatings containing only 5%(mass fraction) Fe-Ni/C composite nanofibers as fillers with thickness of 1.2—2.0 mm exhibit excellent electromagnetic wave absorbing performances, and the reflection loss(RL) exceeding -20 dB can be obtained over the range of 7.4—18 GHz. The microwave absorption properties for the as-prepared nanocomposites are gradually enhanced with increasing the carbonization temperature from 800 ℃ to 1200 ℃ due to the better impedance match, accompanying with a decrease of the minimum RL values from -22.6 dB to -63.0 dB. Overall, the results reveal that the as-prepared Fe-Ni/C composite nanofibers can be a promising candidate for microwave absorbing materials with strong-absorption, light-weight and thin-thickness in X and Ku bands.

    Analytical Chemistry
    Simple and Rapid Determination of Mercury Ions Based on 1,4-Dithiothreitol Assembled Gold Plate Electrode
    CAO Tingting, CAO Zhong, HE Jinglin, LIANG Haiqin, XIAO Zhongliang
    2014, 35(7):  1388-1395.  doi:10.7503/cjcu20140288
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    A simply gold plate electrode(GPE) based on 1,4-dithiothreitol(DTT), which was self-assembled on a surface of flat gold film with a thickness of 100 nm, was developed to construct a novel selective electrode method for rapid detection of mercury ion. Through electrochemical impedance analysis and cyclic voltamme-tric method, the response mechanism of the electrode for selective recognition of Hg2+ was investigated, that the other terminal sulfhydryl group of DTT binding to Au surface can coordinate with Hg2+ due to their strong complexing interaction, resulting in change of membrane potential of the electrode surface. The proposed electrode possesses good potential performance responding to Hg2+ with a linear range of 1.0×10-8—1.0×10-3 mol/L, a Nernst slope of (29.62±0.2) mV/-pc(25 ℃), and a detection limit of 5.1×10-9 mol/L in Tris-HCl buffer solution(pH=6.0). The electrode has short response time(20 s), good reproducibility and stability. No interference can be observed from most common ions like Cu2+, Fe2+, Na+, K+, Mg2+, Ba2+, Ca2+, Zn2+, Sn2+, Pb2+, Ag+, Al3+, Fe3+, Ni2+, NO2-, IO3-, BrO3- and ClO3-. Compared with spectrophotometric method with dithizone, the proposed electrode can be well utilized to the determination of trace amount of Hg2+ in real water samples with a recovery rate of 98.20%—101.75%, showing promising application in environmental and other fields.

    Studies on the Isoflavone in Extract of the Flower of Pueraria Lobata by RRLC-Q-TOF MS/MS
    DAI Yulin, YU Shanshan, ZHANG Ying, HAO Ying, ZHONG Wei, YUE Hao, LIU Shuying
    2014, 35(7):  1396-1402.  doi:10.7503/cjcu20140168
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    Rapid resolution liquid chromatography-electrospray ionization mass spectrometry(RRLC-ESI-MSn) was applied to identify and differentiate the isoflavone constituents of the flower of Pueraria lobata(Willd.)Ohwi. The data of retention time and molar masses were obtained for the identification of the major isoflavone constituents in the flower of Pueraria lobata(Willd.) Ohwi. The ESI-MSn data of the [M-H]- provide detailed structural information on the isoflavone. Alopecuroides A has been firstly detected from the Pueraria lobata(Willd.) Ohwi. flower. 28 components were detected in total from the flower of Pueraria lobata(Willd.) Ohwi..

    Rapid Measurement of Synthetic Pigments by Thermal Desorption-High Field Asymmetric Waveform Ion Mobility Spectrometry(FAIMS) Technology
    LI Juan, ZHAO Weijun, LI Lingfeng, LI Xin, LI Peng, WANG Xiaozhi
    2014, 35(7):  1403-1408.  doi:10.7503/cjcu20140139
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    Field asymmetric ion mobility spectrometry(FAIMS) technique was introduced into the sensitive and rapid analysis of four synthetic pigments for the first time. The chrysoidin, malachite green, rhodamine B and methyl red were detected by a co-developed thermal desorption-FAIMS(TD-FAIMS) system. The ion characteristic signals of synthetic pigments were acquired under the optimized conditions with the injection temperature of 160 ℃ and the carrier gas flow rate of 1.6 L/min. Compensation voltage(CV) values with different modes were adopted for qualitative measurement. FAIMS detection signals in positive mode appeared at CV=0.41 and 0.89 V for chrysoidine and rhodamine B, respectively, while negative mode detection signals of methyl red and malachite green appeared at CV=0.67 and 0.02 V, respectively. Using external stan-dard method for quantitative measurement, the linear relationship(R2) was above 0.9967. The limits of detection(LOD) were 2.5—10 μg/L, and limits of quantification(LOQ) were 5—20 μg/L, respectively. The average recoveries were higher than 78.2% and the relative standard deviation(RSD) was less than 8.0%. This study laid a foundation for the application of FAIMS technique to rapid detection of synthetic pigments. The FAIMS instrument, which are highly sensitive, simple and fast responsive, demonstrated huge potential in the rapid analysis of synthetic pigments.

    Enantioseparation of Underivatized D,L-Serine in Biological Matrices by Capillary Electrophoresis with Contactless Conductivity Detection
    WEI Yu, CHEN Yufu, ZHOU Qiang, YUAN Qiuyue, TAN Fengyu, XIE Tianyao
    2014, 35(7):  1409-1413.  doi:10.7503/cjcu20140109
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    A new method for enantioseparation of underivatized D,L-serine in biological matrices by capillary electrophoresis with contactless conductivity detection using binary chiral selectors(Cu-L-Arg and HPMC) was developed.The enantiomers of D,L-serine could reach an excellent baseline separation in an uncoated fused-silica capillary(50 μm i.d.×45 cm, Leff=40 cm) under the chosen separation conditions and using 3.2 mmol/L NaOH+0.4 mmol/L Cit+2.5 mmol/L Cu(Ac)2+5.0 mmol/L L-Arg +15.0 mg/L HPMC(pH=9.8)as the running buffer. The calibration curve of the enantiomers showed good linearity in the range of 0.35—30 mg/L with a limit of detection(LOD) of 0.10 mg/L. Effects of several factors on resolutions, such as the composition of the running buffer, pH, separation voltage and injection method were investigated to acquire the optimum conditions. The proposed method, without derivatization, has been applied to determine the D-serine contents in rat brain tissue, and was demonstrated simple, efficient, cost-effective and reproducible.

    Enantioseparations of Dihydropyridine Drugs by Sulfobutyl Ether-β-Cyclodextrin Modified Capillary Electrochromatography
    NIE Guizhen, LI Laisheng, CHENG Biaoping, ZHOU Rendan, ZHANG Hongfu
    2014, 35(7):  1414-1422.  doi:10.7503/cjcu20140099
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    A novel sulfobutyl ether-β-cyclodextrin(SBE-β-CD) capillary electrochromatographic column(SECDP) was prepared by glycidyl methacrylate polymer matrix in situ and its modification. Its basic structure was characterized by infrared spectroscopy(IR) and scanning electron microscopy(SEM). The sulfonic acid group could provide a enough and stable positive electroosmotic flow(EOF). Enantioseparations of 10 kinds of chiral dihydropyridine drugs including amlodipine, nimodipine, nicardipine and so on were achieved by synergistic effects of SBE-β-CD in the stationary and mobile phases. Some effect factors such as the chiral additive concentration, pH value, the applied voltage, temperature and organic modifier content were optimized. The optimal separation conditions were as follows: the mobile phase consisting of 20 mmol/L NaH2PO4(pH=4.0), containing 4.0 mmol/L of SBE-β-CD, acetonitrile volume content of 10% to 25%, an applied voltage of 15—25 kV, the temperature at 15 ℃, electrokinetic injection 2 kV×5 s and the detection wavelength at 236 nm. Under the above conditions, the separation resolutions(Rs) of dihydropyridine enantiomers were up to 3.62, the column efficiency were about 61011/m, and the analysis time were generally between 6—15 min. Based on the data of chromatographic separations, the related chiral separation mechanism was also discussed. The preparation method of SECDP and chiral separation method were rapid, simple, reprodu-cible and suitable for fast enantioseparations and montoring of chiral dihydropyridine drugs.

    Organic Chemistry
    Anti-complementary Activities of a (1→6) Linked Glucan from Korean Mondshood Root and Its Sulfated Derivatives
    LI Xiaojun, JIANG Jiaye, SHI Songshan, LI Yuan, JIANG Yongbo, KE Yan, WANG Shunchun
    2014, 35(7):  1423-1426.  doi:10.7503/cjcu20131268
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    In order to study anti-complement activity in the classical pathway of Korean Mondshood root and its sulfated polysaccharides, a homogeneous polysaccharide(KMPS-2A) was gained from the Korean Mondshood root[Aconitum coreanum(Lévl.) Raipaics] by water extract and alcohol precipitate via DE-32, Superdex-200 and Superdex-75 gel filtration. Its structure was investigated by high performance gel permeation chromatography, methylation analysis, NMR and IR spectrometry. The results showed that the average molecular weights(Mw) of the KMPS-2A was 676000 and it was consisted of a repeating structure as [α-1,6-D-Glc]n. Sulfated derivatives were gained by chlorosulfonic acid-pyridine method and it was found that the sulfated derivatives had the highest degree of substitution(1.79) when the volume ratio of chlorosulfonic acid and pyridine was 1.75∶1.0. It was shown that sulfated polysaccharide 1.75B had a better anti-complementary activity. C2, C3 and C4 were substituted by sulfate groups. A certain correlation was presented between the degree of substitution and the anticomplementary activity of sulfated derivatives. Anticomplementary activity of sulfated derivative 1.75B was better than the heparin group in the classical pathway, which suggested the potential activity of the complement inhibitors.

    Synthesis and Biological Activity of 1,3,4-Oxadiazole Mannich Bases Containing Pyrimidine Rings
    SHEN Shengqiang, SUN Xiaohong, LIU Yuanfa, CHEN Bang, JIN Ruyi, MA Haixia
    2014, 35(7):  1427-1432.  doi:10.7503/cjcu20131254
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    1,3,4-Oxadiazole derivatives were reported to possess a broad spectrum of biological activities, such as antifungal, antibacterial, antiviral and antitubercular. Mannich bases had also been reported as potential biological agents, they were applicated in the fields of synthetic study and medicinal chemistry. In recent years, Mannich bases containing 1,3,4-oxadiazole ring had attracted a lot of attention and many Mannich bases of 1,3,4-oxadiazole bearing heterocycle scaffold were reported to have special bioactivity. Nevertheless, literature revealed that there were no reports of a molecular scaffold that Mannich base of 1,3,4-oxadiazole bearing pyrimidine. Prompted by these observations, a series of 1,3,4-oxadiazole derivatives containing pyrimidine(E1—E15) was synthesized from 5-aryl-1,3,4-oxadiazole-2-thione(C1—C3), formaldehyde and substituted aminopyrimidine(D1—D5) by Mannich reaction. 5-Aryl-1,3,4-oxadiazole-2-thione derivatives(C1—C3) were prepared from aromatic acids as the starting material via esterification, hydrazinolysis and cyclization. The structures of all title compounds were confirmed by elemental analysis, IR, 1H NMR techniques. Furthermore, their biological activities to four vegetable pathogens containing Gibberll nicotiancola, Gibberlla saubinetii, Fusarium oxysporium f. sp. niveum, Pythium solani had been tested. The preliminary results indicated that most of the compounds exhibit relatively good fungicidal activities, especially compounds E3 and E8 showed better biological activity than triazolone.

    Syntheses and Properties of Four-ring Liquid Crystals with Ethylene and Internal Alkyne Bridge
    CHEN Ran, AN Zhongwei, CHEN Xinbing, CHEN Pei
    2014, 35(7):  1433-1438.  doi:10.7503/cjcu20131233
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    Ten four-ring liquid crystals with ethylene and internal alkyne bridge were synthesized via Grignard reaction, Huang Minglong reduction, iodination, “one-pot” Sonogashira cross-coupling reaction with trans-4-alkyl-cyclohexane-carboxylic-acid as the starting substrate. The structures of the compounds were confirmed by infrared spectrometry(IR), nuclear magnetic resonance(NMR) and mass spectra(MS). The differential scanning calorimetry(DSC), polarising optical microscopy(POM) and Abbe refractometer were used to measure their properties. The results show that the compounds possess high clearing point(220—240 ℃), broad nematic phase(59.6—99.6 ℃) and high birefringence(Δn>0.3). These properties match the requirement of liquid crystal optics.

    Syntheses and Optical Properties of Two Novel Terpyridine Derivatives
    GAO Yuanhao, PAN Ruilong, TIAN Yupeng, LI Jing, ZHENG Zhi
    2014, 35(7):  1439-1444.  doi:10.7503/cjcu20131226
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    Two novel D-π-A type terpyridine derivatives with two-photon properties were synthesized using 2,2'∶6',2″-terpyridine as the acceptor(A) and other functional groups as the donor(D). For the two D-π-A type terpyridine derivatives, their linear absorption, single- and two-photon properties were measured. These results show that the target compounds have good fluorescence with the fluorescence quantum yield(Ф)up to 0.45 and the maximal two-photon absorption cross section(δ2) up to 406 GM at 830 nm. Theoretical calculations were consistent with the experimental results.

    Synthesis and Bioactivity of 1,4-Bis[3-aliphatic/aryl -1,2,4-triazole[3,4-b]-1,3,4-thiatriazole-6-yl] Aryl Derivatives
    ZHANG Chenglu, SUN Lijie, WU Feiyu, QU Ruifeng, ZHU Chang’an, WANG Xue, CHAI Jinhua, GUO Yang, HU Xue
    2014, 35(7):  1445-1450.  doi:10.7503/cjcu20131194
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    Fourteen new bis-1,2,4-triazole[3,4-b]-[1,3,4]thiadiazol-6-yl derivatives(2 and 3) were synthesized in high yields through the reactions of six 3-aliphatic-1,2,4-triazole derivatives(1a—1f) and 3-phe-nyl-1,2,4-triazole(1g) with terephthalic acid and 2-aminoterephthalic acid, respectively, in the presence of phosphorus oxychloride. The structures of target compounds were characterized and the inhibitory properties of Cdc25B and PTP1B were studied. The results showed that compounds 2f, 3a and 3g exhibited high inhibitory activity against Cdc25B enzyme with IC50 values of (3.45±0.60), (0.69±0.10) and (1.52±0.19) μg/mL, respectively. Compounds 3a and 3b showed high inhibitory activity against PTP1B with IC50 values of (0.98±0.13) and (2.00±0.16) μg/mL.

    Synthesis and Fungicidal Activity of Novel Daphneolone Analogues
    XIE Ruilong, SONG Yue, YANG Xinling, WANG Meizi, LING Yun
    2014, 35(7):  1451-1457.  doi:10.7503/cjcu20131138
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    Taking the natural product(E)-1,5-diphenylpent-2-en-1-one(A) from Stellera chamaejasma L. as the lead compound, 15 novel daphneolone derivatives containing chromone fragments were designed and prepared base on the previous work. Their structures were confirmed by Fourier transform infrared(FTIR) spectroscopy, 1H and 13C nuclear magnetic resonance(1H NMR, 13C NMR) spectrometry and elemental analysis or high-resolution mass spectrometry(HRMS). The preliminary bioassay results indicated that some compounds showed moderate to good fungicidal activities. Some target compounds showed better activity than lead compound A at 100 mg/mL. Especially, compound 6d, with inhibition rates of 87% and 86% against Rhizoctonia solani and Botrytis cinerea respectively, exhibited comparable activity with the control difenoconazole and was valuable for further optimization.

    α,β-Vicinal Bromoamine Compounds Converted into α,β-Dehydroamino Derivatives Promoted by Combination of Potassium Carbonate and Thiouea in Water
    CHEN Zhanguo, WANG Yingjie, LIU De’e, LIU Yali, LI Ya’nan, WANG Dan, GE Miao
    2014, 35(7):  1458-1464.  doi:10.7503/cjcu20131129
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    In order to promote further development of green chemistry, an easy and efficient new method for the synthesis of fuctionalized enamines from α,β-vicinal bromoamine compounds promoted by combination of potassium carbonate and thiouea in water at room temperature was developed, and the nearly quantitative yields of much products were obtained(up to 99%). 23 structurally different substrates were investigated. The results indicate that the protocol could tolerate various vicinal bromoamine compounds including α,β-vicinal bromoamine esters and ketones. During the elimination process of HBr from vicinal bromoamine compounds, the corresponding intermediate aziridines must be formed. Herein, no matter the substrate was α-amino-β-bromo or α-bromo-β-amino in structurally, the aziridines skeleton in structurally was similar to each other formed from the intramolecular nucleophilic replacement reaction fashion. Because of ring-open reaction of the aziridines have full regiospecificity, the obtained final products are full regiospecificity, too. The structures of all products were confirmed by 1H NMR, 13C NMR and HRMS analysis. When the gram level substrate was tested with this protocol, the nearly quantitative yield of the product was obtained, too. This result indicated that the new method could be possible applied in the industrialization.

    Syntheses and Anticancer Activities of Glycine Derivatives of Chrysin
    SONG Xiudao, HE Jun, MA Jin, LIU Yunmei, ZHENG Xing, LEI Xiaoyong, GUO Yu
    2014, 35(7):  1465-1470.  doi:10.7503/cjcu20131126
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    In order to obtain novel lead compounds with high efficacy, low toxicity and minimum of side effects, using chrysin(5,7-dihydroxyflavone) with very broad biological activities as a starting material, four intermediates 7-O-carboxyalkylation chrysin derivatives(6—9) were synthesized by halogenation and hydrolysis. Four glycine methyl ester derivatives containing chrysin(12—15) were synthesized when the four intermediates above condensated with glycine methyl ester hydrochloride using 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride(EDCI), N-hydroxybenzotriazole(HOBt) and 4-dimethylamiopryidine(DMAP) as a coupling reagent. And then the corresponding glycine derivatives of chrysin(16—19) were obtained by hydrolysis under conditions of room temperature and pH 10—11. The structures of the target compounds were assigned by 1H NMR, 13C NMR, IR and MS. Taking cisplatin as a reference substance, the in vitro antitumor activity tests for target compounds against human hepatocellular carcinoma HepG2 cells and gastric carcinoma MGC-803 cells were carried out by MTT method. The results of primary pharmacological tests indicated that five compounds(14—16, 18, 19) possessed the more potent antitumor activity than chrysin in vitro. What’s more, the antitumor activity of compound 18(IC50=4.36 μmol/L) against MGC-803 cells was better than the positive reference compound cisplatin(IC50=4.40 μmol/L).

    Physical Chemistry
    Theoretical Studies on the Carrier Transport Properties of Halogen, Cyan Group and N-atom Modified Tetrathiafulvalene Derivatives
    LI Qian, GENG Yun, DUAN Yuai, WANG Guangyu, SU Zhongmin
    2014, 35(7):  1471-1479.  doi:10.7503/cjcu20140210
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    The density functional theory and hopping model with band theory were employed to calculate the charge carrier transport properties of six planar polycyclic aromatic hydrocarbon fused tetrathiafulvalene(TTF) derivatives. The effects of halogen, cyan substitutions and nitrogen were investigated in details. It was confirmed that the introduction of N-atoms reduced the molecular reorganization energy especially when the N-atoms were modified next to the TTF core. Comparing to the halogen the cyan group modified molecules behave lower reorganization energy and lower frontier energy level. The calculated electron drift mobility of molecule 6 is 1.15 cm2·V-1·s-1. More over the molecule maintains the lowest LUMO energy level, implying that the molecule may exhibit good electron transport property. The calculated electron dirft mobility(0.37 cm2·V-1·s-1) of molecule 2 is very close to hole dirft mobility(0.34 cm2·V-1·s-1), indicating molecule 2 is suitable for bipolar devices. Moreover, the weak interactions of S…S, S…N and N…N between molecules in crystal were inspected. The results show that the introduction of S or N atom contributes to HOMO(or LUMO), leading to an increase of hole(or electron) transport property.

    Primary Photocalorimetry Investigation of the In-situ Photocatalytic Process of Methyl Orange Degradation
    LI Xingxing, HUANG Zaiyin, FAN Gaochao, WU Yenan, TAN Xuecai
    2014, 35(7):  1480-1483.  doi:10.7503/cjcu20140176
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    Ag@AgCl photocatalyst was prepared by reduction of AgCl precursor at room temperature, and characterised by X-ray powder diffraction(XRD) and field-emission scanning electron microscope(FE-SEM). A novel photoreaction-microcalorimetry was designed and employed to obtain the on-line thermodynamic and kinetic informations of photocatalysis of methyl orange over Ag@AgCl. The results showed that the degradation process went through an initial endothermic reaction and followed by an exothermic stage which finally kept a constant exothermic rate for at least 4 h. The heat effects of ab, ac, and ad stages were -0.2609, 2.5845 and 40.7289 J, respectively. Meanwhile, the steady rate of exothermic platform, the stage of cd, is 2.581 mJ/s. The microscopic mechanism of photodegradation was discussed in detail.

    Preparation, Characterization and Antibacterial Adhesion Performance of the Biomimetic Surfaces via Zwitterionic Self-assembly
    WU Yalu, LI Guangji, LIU Yunhong, CHEN Dayang
    2014, 35(7):  1484-1491.  doi:10.7503/cjcu20140160
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    A sulfobetaine zwitterionic compound, N,N-dimethylamino ethyl carbamate propyl triethoxysilane sulfonate(SiNNS), was designed and synthesized and its composition and molecular structure were characterized by means of FTIR and 1H NMR spectroscopy. Furthermore, the biomimetic surface imitating the chemical features of cellular outer membrane were constructed via the self-assembly of SiNNS molecules on the hydroxylated glass surface. The morphology structure, chemical composition and wettability of the prepared biomimetic surface were characterized by atomic force microscopy(AFM), X-ray photoelectron spectroscopy(XPS) and contact angle measurement. The antifogging and antibacterial adhesion performances of the biomimetic surface were investigated using an untreated glass surface as a control sample. The results indicate that the zwitterionic self-assembled biomimetic surface can possess superhydrophilicity with a water contact angle of 9.2° and underwater superoleophobicity with an oil contact angle of 175.6°. Compared to the corresponding control sample, the zwitterionic self-assembled biomimetic surface can exhibit an excellent antifogging property and an obvious antibacterial adhesion performance.

    Mechanism Studies on Adsorption of DNA Bases and Base Pair-Zn2+ mplexes for CO2, N2 and H2
    SHI Shuai, HUANG Ximing, AI Hongqi
    2014, 35(7):  1492-1499.  doi:10.7503/cjcu20140137
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    As an intriguing material building block for microporous metal-organic framework(MOF) materials, DNA base(pair) holds usually rigid-ring structures, multiple metal coordination sites, biological compatibility, and molecular recognition as well as self-assembling characteristics that could ultimately translate into interesting material properties. In the present paper, guanine G, cytosine C, adenine A, thymine T, and their pairs GC/AT as well as their Zn2+ complexes were selected as models to study their potential behavior of building block to adsorb mixed small molecules H2, N2, CO2 by employing M062X/6-31+G* method. The interaction modes and strengths as well as potential binding sites were predicted. These results reveal that CO2 prefers H-bonding to the amino hydrogen(s) or/and imino hydrogen(s) of these bases(pairs), whereas both H2 and N2 prefer being adsorbed over the base ring with a π-stacking interaction mode. A comparison for the binding energies of these different small molecules shows that AT is the more potential building block of MOF material than GC and AA, and will adsorb these small molecules hierarchically according to the following order: H2 < N2 < CO2. The result offers theoretical predictions and direction for the experimental synthesis of such MOF materials built by these different base-pair building blocks.

    Theoretical Studies on the Conjugate Addition of 1-Bromonitromethane to Benzylidene Acetone Catalyzed by 9-Amino-9-deoxyepiquinine
    JIANG Haiyang, FENG Wei, SUN Yanwei, QI Qiaofang, TIAN Hongwei, LIU Huiling, HUANG Xuri
    2014, 35(7):  1500-1509.  doi:10.7503/cjcu20140136
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    Asymmetric conjugate addition of 1-bromonitromethane tobenzylidene acetone was catalyzed by 9-amino-9-deoxyepiquinine as organic catalyst and benzoic acid as co-catalyst. We had identified a detailed mechanism of the title reaction with density functional theory(B3LYP and M062X) and ab initio calculations(MP2). The reaction process includes three major stages: (1) the formation of an iminium ion intermediate; (2) the nucleophilic addition between the iminium and 1-bromonitromethane; (3) hydrolysis and recovery of catalyst. The calculated results not only explain benzoic acid as acidic additive plays an important role in the formation of the key reaction iminium intermediate, but also provide a general model to help explain the mechanism and enantioselectivity of the conjugate addition reaction.

    Fabrication and TXL Anti-cancer Drug Delivery of Magnetic Mesoporous Silica Nanoparticles
    ZHANG Zhuoqi, GENG Haoran, XUAN Ruifei, CHEN Minmin, CHEN Hui, LIU Aihui, CAO Xichuan
    2014, 35(7):  1509-1514.  doi:10.7503/cjcu20140122
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    Magnetic Fe3O4@SiO2 mesoporous silica nanoparticles(MSNs) were synthesized with Fe3O4 nanoparticles as crystal core, cetyltrimethylammium bromide(CTAB) as structural directional agent through the hydrolysis of tetraethoxysilane(TEOS) and self-assembly procedure under the basic conditions. The synthesized MSNs were characterized via the XRD, FTIR, TEM and N2 adsorptiom-desorption. The results show that these MSNs have high sepcific surface area of 932 cm2/g, particles size of 150 nm and typical hexagonal packing mesoporous structure. Simultaneously, all Fe3O4 nanoparticles are perfectly embedded in silica bulk. As a TXL carrier, Fe3O4@SiO2 exhibits good adsorption with the maximum adsorption capacity of 80 mg/g and TXL-Fe3O4@SiO2 has a more than 120 h sustained release for TXL with accumulative quantity of 30 mg/g. While the release behaviour is controlled by various pH values. Higher the pH is, larger the accumulative release is. Experiments of cytotoxicity on HeLa cells indicate that the Fe3O4@SiO2 particles exhibit excellent biocompatibility. TXL-Fe3O4@SiO2 shows significant inhibition effect on HeLa cells than bare TXL under the same drug concentration.

    H2S Absorption Capacity of Ionic Liquid-MDEA-H2O Combined Desulfurizers
    MA Yunqian, WANG Rui
    2014, 35(7):  1515-1522.  doi:10.7503/cjcu20140108
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    Three kinds of functionalized ionic liquids [Bmim]HCO3, [TMG]L and [MEA]L were synthesized. The structure and thermostability of the synthetic ionic liquids(ILs) were confirmed by FTIR spectrum and thermogravimetry characterization, respectively. The new combined desulfurizers were prepared by mixing ionic liquid([Bmim]HCO3, [TMG]L, [MEA]L, [Bmim]Cl or [Bmim]BF4) with methyldiethanolamine(MDEA) aqueous solution according to certain proportion. Under conditions of different ionic liquids, absorption temperature and desulfurizer composition, H2S absorption and bubble eliminating capacity of the desulfurizer were measured, and regeneration performance of the favorable desulfurizer was studied. The concentration of SO42- in regenerated desulfurizer was analyzed by ion chromatography after deep oxidation by O3, and the mechanism of absorption was analyzed based on the calculations from density functional theory. The results show that absorption capacity is in the sequence of [Bmim]Cl-MDEA-H2O>[Bmim]HCO3-MDEA-H2O>[Bmim]BF4-MDEA-H2O>MDEA-H2O>[TMG]L-MDEA-H2O>[MEA]L-MDEA-H2O, and the major factor is attributed to the stability of IL-MDEA; [Bmim]HCO3 performs the best capacity of bubble elimination; [Bmim]Cl-MDEA-H2O, [Bmim]HCO3-MDEA-H2O and [Bmim]BF4-MDEA-H2O can be nearly completely regenerated by air, and high stability of IL-H2S leads to higher absorption efficiency, but smaller extent of regeneration.

    Preparation and Visible-light Catalytic Property of Ag+/Ag/ZnOPorous Nano-structured Fiber Materials
    SHAO Kerang, LI Jianjiao, AN Xingcai, LEI Ziqiang, SU Bitao
    2014, 35(7):  1523-1528.  doi:10.7503/cjcu20140065
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    Ag+/Ag/ZnO porous nano-structured fiber materials were prepared by the template-assisted two-steps method and characterized by thermogravimetric analysis(TG), X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), scanning electron microscopy(SEM) and UV-Vis spectroscopy(UV-Vis) techniques. The effect of modified silver amount(molar fraction, 0—1.5%) on the photocatalytic property of ZnO materials was studied by the degradation of methylene blue(MB) as the model reaction. The results show that the Ag+-Ag co-modified ZnO porous nano-structured fiber materials are successfully prepared via the template-assisted two-steps method and the Ag+-Ag co-modifification affects the photocatalytic performance of ZnO materials by affecting its cell structure and light adsorption property and morphology. Under the irradiation of visible light, the Ag+/Ag/ZnO porous nano-structured fiber materials showed better catalytic performance than pure ZnO and the catalytic perfrmace of Ag+/Ag/ZnO is related to the modified amount of Ag+-Ag. In this paper, the way of Ag+ and Ag for improving photocatalytic performance of the ZnO materials was discussed. And the obtained results are helpful to understand the photocatalytic phenomena and mechanisms on the multi-structured material.

    Biocatalytic Asymmetric Oxidation of Racemic 1-(4-Methoxyphenyl) Ethanol Using Immobilized Acetobacter sp.CCTCC M209061 Cells in Organic Solvent-containing Biphasic System
    CHENG Jing, LOU Wenyong, ZONG Minhua
    2014, 35(7):  1529-1535.  doi:10.7503/cjcu20140058
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    The resolution of racemic 1-(4-methoxyphenyl) ethanol(MOPE) to enantiopure(S)-MOPE through highly enantioselective oxidation of MOPE with immobilized Acetobacter sp.CCTCC M209061cells was successfully conducted in organic solvent-containing biphasic system. In spite of exhibiting relatively slower reaction rate than free cells, immobilized cells of Acetobacter sp.CCTCC M209061 showed much higher stability, including operational stability, thermal stability and storage stability. The immobilized cells still retained more than 58% of its original catalytic activity after being repeatedly used for 10 batches(12 h per batch), and the free cells maintained only around 20% of relative activity. Among various organic solvents examined, use of n-hexane as the second phase in a two-phase system enhanced the concentration of substrate, the initial reaction rate, the enantiomer recovery and the residual substrate e.e., resulting from its excellent ability to dissolve MOPE and good biocompatibility with Acetobacter sp.CCTCC M209061 cells. As a result, n-hexane was selected as the most suitable organic phase for the reaction. For the biocatalytic oxidation of MOPE carried out in n-hexane-based biphasic system, the optimum volume fraction of n-hexane, co-substrate and its concentration, substrate concentration, buffer pH and reaction temperature were 60%, 50 mmol/L acetone, 40 mmol/L, 6.5 and 30 ℃, respectively. Under the above-described optimized reaction conditions, the initial reaction rate was 80.4 μmol/min, the enantiomer recovery and the residual substrate e.e. reached 51.0% and 99.9% at reaction time of 12 h, respectively, which were better than the results obtained in aqueous monophasic system.

    Synthesis and Ethylene Oligomerization Catalytic Activities of Hyperhranched Salicylaldehyde-imine Nickel Complex
    WANG Jun, YANG Guang, LI Cuiqin, SHI Weiguang
    2014, 35(7):  1536-1540.  doi:10.7503/cjcu20131299
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    A novel hyperbranched salicylaldehyde-imine nickel complex was prepared and characterized via elemental analysis, electrospray ionization-mass spectrometry(ESI-MS), Fourier transform infrared spectrometry(FTIR), UV-Vis spectrometry(UV-Vis), 1H nuclear magnetic resonance(1H NMR) and 13C nuclear magnetic resonance(13C NMR) spectrometry. This hyperbranched complex was evaluated as catalyst precursor in the oligomerization of ethylene, using methylaluminoxane(MAO) as an activator. The effects of the Al/Ni molar ratio and polymerization temperature on the catalyst activity and product distribution were investigated. The results show that the catalyst possesses a middle catalytic activity of 5.59×105 g/(mol Ni·h) with a selectivity for higher olefins(C10—C18) of 91%.

    Synthesis of Ag/mSiO2 Hollow Microspheres for SERS-tags
    REN Zhiyu, LI Zhongtao, DU Shichao, WU Jun, KONG Lingjun, FU Honggang
    2014, 35(7):  1541-1545.  doi:10.7503/cjcu20131252
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    Ag/mSiO2 hollow microspheres were synthesized via the following steps. Monodisperse polystyrene(PS) colloidal microspheres were coated with Ag nanoparticles through in situ reduction and growing seeds. The composite microspheres were then controllably coated with mesoporous silica shell using cetyl trimethyl ammonium bromide(CTAB) as pore-forming agent. After getting rid of template, Ag/mSiO2 hollow microspheres were obtained. To actualize SERS-tags detection, the hollow microspheres were subsequently tagged with 4-ATP via siphonage effect. Due to the air-resistance effect of mesoporous channel and light’s multiple scattering in the interior of hollow microspheres, the obtained SERS-tags material showed low limit of detection and high stability.

    Preparation of Sulfonated Graphene/Activated Carbon Composite Electrode for Asymmetric Capacitive Deionization
    LU Miao, LIU Jianyun, WANG Shiping, CHENG Jian
    2014, 35(7):  1546-1552.  doi:10.7503/cjcu20131177
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    Sulfonated graphene(GP-SO3H) was prepared by grafting reaction of sulfonated diazoniun salt. The sulfonated graphene was characterized by Fourier transform infrared spectrometry(FTIR) and scanning electron microscopy(SEM), respectively. The experimental results indicate that the sulfonic groups have been grafted onto graphene oxide. The sulfonated graphene/activated carbon composite electrode(GP-SO3H/AC) was prepared by mixing 10%(mass fraction) GP-SO3H as dopant. Compared with AC electrode, this composite electrode exhibits an ideal double layer capacitive behavior and high conductivity, confirmed by cyclic voltammetry and electrochemical impedance spectroscopy. The hybrid capacitor was assembled by the resultant GP-SO3H/AC as negative electrode and AC as counter electrode for capacitor deionization(CDI). Under the constant current charging-discharging condition, the salt removal amount of 10.87 mg/g in single cycle was obtained, about 2.4 times that of the normal AC capacitor. And the current efficiency was improved dramatically owing to the facile adsorption of sulfonic groups to cations, and the shielding effect of sulfonic groups on the counter-ions. The asymmetric capacitor is expected to be used for actual application in brackish water desalination.

    Polymer Chemistry
    Three-arm Stereocomplexed PPO-PDLA-PLLA Copolymer with High Molecular Weight
    LI Wei, MA Yan, LI Yuanxiang, FAN Zhongyong
    2014, 35(7):  1553-1558.  doi:10.7503/cjcu20140301
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    Three-arm poly(propylene oxide)(PPO) was used as a macroinitiator for the ring-opening polymerization(ROP) of D-lactide to obtain three-arm poly(propylene oxide)-block-poly(D-lactic acid)(PPO-PDLA). PPO-PDLA copolymer was then reacted with stannous octoate [Sn(Oct)2] to obtain Sn(Oct) end-capped PPO-PDLA[PPO-PDLA-Sn(Oct)]. The PPO-PDLA-Sn(Oct) can be used as an efficient macroinitiator for the ROP of L-lactide to synthesize three-arm PPO-PDLA-PLLA at 130 ℃, which reduces the occurrence of hydrolysis and transesterification reaction. PPO-PDLA-PLLA copolymers with high molecular weight were synthesized by this novel and simple method. The results show that the composite of PPO-PDLA-PLLA can be easily tuned by controlling the feed ratio of L-lactide and D-lactide, and the stereoregularity of PPO-PDLA-PLLA is high. Moreover, the stereocomplexes of PPO-PDLA-PLLA can survive melting to reform the stereo-complex crystallites.

    Polymerization of Methyl Methacrylate with α-Diimine Nickel(Ⅱ)
    ZHANG Danfeng, LI Sen, YU Wen, MENG Jiangang
    2014, 35(7):  1559-1564.  doi:10.7503/cjcu20140298
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    Four α-diimine nickel(Ⅱ) complexes: [(t-Bu)—NCH—CHN—(t-Bu)]NiBr2(C1), [C6H5—NC(Me—C(Me) N—C6H5]NiBr2(C2), [(2,6-C6H3(Me)2)—NC(Me)—C·(Me) N—(2,6-C6H3(Me)2)]NiBr2(C3) and [(2,6-C6H3(i-Pr)2)—NC(An)—C(An) N—(2,6-C6H3(i-Pr)2)]NiBr2(An=acenaphthyl)(C4), in the presence of methylaluminoxane(MAO) as cocatalyst, were applied in the polymerization of methyl mathacrylate(MMA). The influence of polymerization parameters, such as molar ratio of Al/Ni, monomer concentration, polymerization temperature and time, as well solvents were studied with complex C2/MAO system. Based on these results, all nickel complexes were compared under optimized polymerization conditions{1.6 μmol catalyst, n(Al)/n(Ni)=800, [MMA]=2.9 mol/L, toluene as solvent, 60 ℃ for 4 h}. In each case, syndiotactic enriched polymer was obtained. The complexes with more bulky frame work exhibit lower catalytic activities, for example, C1 with the smallest bulky frame work gives the highest activity, 107.8 kg/(mol Ni·h) while C4 with the biggest bulky frame work gives the lowest activity, 7.8 kg/(mol Ni·h); The complexes with more electronic donor substituents exhibit higher activities and molecular weight of PMMA. The activity of C2 is 62.5 kg/(mol Ni·h), and the molecular weight of PMMA is 5.0×104, while that of C3 is 96.9 kg/(mol Ni·h) and produce higher molecular weight of PMMA(7.6×104).

    Influence of the Polymer with High Molecular Weight on the Solvent-induced Dewetting Dynamics of the Polymer Thin Film with Low Molecular Weight
    LIU Hui, ZHENG Yisong, SHI Tongfei
    2014, 35(7):  1565-1569.  doi:10.7503/cjcu20140278
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    The dewetting dynamics of the polystyrene(PS) thin film induced by the solvent of acetone with the method of optical microscopy(OM) and Ellipsometer were investigated. We compared the dewetting dynamics of the monodiperse PS with low molecular weight(PSL), that with high molecular weight(PSH) and the mixture of the PSL and PSH(PSM). It was observed that their dewetting behavior was different although the radius of the holes vs. time exhibited exponential behavior for all samples. As for monodiperse PS, there is the difference in rim morphologies because of the viscosity difference between the PSL and the PSH. As for the PSM, the anomaly of the deweting velocity with the addition of PSH happens due to effect of the chain connectors which were partially in the entangle polymer film and partially in the top film.

    Dual-responsive Micelles Based on Boronicacid-modified Polymer
    SUN Xiaocheng, YANG Hao, WANG Jianzu, MA Rujiang, AN Yingli, SHI Linqi
    2014, 35(7):  1570-1578.  doi:10.7503/cjcu20140270
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    Phenylboronic acid modified polymer poly(ethylene glycol)-b-poly(aspartic acid-co-aspartamidophenylboronic acid)[PEG-b-P(Asp-co-AspPBA)] as well as a cross-linker 3,3'-dithiobis[1,2(S)-propanediol](DTBPD) which contained disulfide bond and dual-diol groups was successfully synthesized. PEG-b-P(Asp-co-AspPBA) could be mildly cross-linked by DTBPD based on the reaction of PBA and the dual-diol groups, leading to the formation of a novel dual-responsive micelle with boronic ester core and PEG shell. The structure, morphology, and the glucose/redox dual-responsive behavior of the micelles were systematically investigated by nuclear magnetic resonance(NMR) spectrum and dynamic laser light scattering(DLS). It was demonstrated that the ratio of diol to PBA(D∶B) had influence on the dual-responsive behavior of the micelles. At higher ratio of D∶B, only responsive swelling of micelles was observed. While for the micelles with lower ratio of D∶B, larger degree of swelling happened and the micelles gradually dissociated under higher concentrations of glucose ordithiothreitol(DTT). This kind of dual-responsive micelles may find application in drug delivery in the future.

    Statistical Properties on the Aggregation of Patchy Particles
    HONG Xiaozhong, GU Fang, LI Jiangtao, WANG Haijun
    2014, 35(7):  1579-1583.  doi:10.7503/cjcu20140174
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    The aggregation of patchy particle with distinct patchy was investigated by the statistical mechanical method, in which the change in some average physical quantities with degree of association was of the particular interest. Specifically, the equilibrium free energy and laws of mass action describing the two types of associations were derived by the constructed partition function, and then the size distribution of patchy clusters was obtained. Based on these results, the number- and weight-average degrees of association, the gelation condition as well as the dependence of pre-gel and post-gel regimes on the patchy number were discussed. Furthermore, the kinetic differential equation for description of the growth of patchy clusters was proposed and used to perform the Monte Carlo simulation. The consistence between simulation and analytical results demonstrate the validity of the kinetic differential equation. An aim is attempted to correlate thermodynamic and dynamic conditions with the degrees of association, and thereby provide possible clue for regulating the aggregated and phase structures of patchy particles.

    Preparation and Gas Separation Properties of Metal-organic Frameworks/Polyimide Mixed Matrix Membranes
    DUAN Cuijia, CAO Yiming, JIE Xingming, WANG Lina, YUAN Quan
    2014, 35(7):  1584-1589.  doi:10.7503/cjcu20140076
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    Three metal-organic frameworks(MOFs) with different structure, particle size and gas adsorption properties were synthesized: micron-scale Cu3(BTC)2, sub-micron ZIF-8 and S-Cu3(BTC)2. Nitrogen adsorption-desorption isotherms of MOFs showed that ZIF-8 and Cu3(BTC)2 possessed quite large BET surfaces(1653 and 1439 m2/g), and BET surface of S-Cu3(BTC)2 was 171.4 m2/g. MOFs were directly introduced into polyimide to fabricate mixed matrix membranes(MMMs). It was proved by XRD and FTIR-ATR characterizations that MOFs had no structural or chemical degradation in MMMs. Gas permeation test result indicated that gas separation properties of MMMs were enhanced as MOFs were added. Comparing with pure polyimide membrane, the adding of ZIF-8 or Cu3(BTC)2 brought gas permeability increase about 3 times, gas permeability of MMMs with S-Cu3(BTC)2 increased 175%. Meanwhile gas selectivies for O2/N2 and CO2/CH4 decreased slightly.

    Preparation and Characterization of the CMC-g-DNAHybrid Copolymers
    LI Min, XING Zhaohui, TIAN Yanzhi, JIANG Yong
    2014, 35(7):  1590-1595.  doi:10.7503/cjcu20140045
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    Sodium carboxymethyl cellulose grafted DNA(CMC-g-DNA) hybrid copolymer, which can be a potential gene drug, was synthesized and characterized by both chemical and biological methods. First, the carboxyl groups on the side chain of CMC were activated by both 1-(3-dimethylaminopropyl)-3-ethylcarbo-diimide(EDC) and N-hydroxy-succinimide(NHS) in phosphate buffer at both neutral and acid condition, respectively. After that, the CMC-NHS reacted with amino-functionalized oligodeoxynucleotides(NH2-ODNs) to get CMC-g-ODNs grafted copolymer. Then CMC-g-ODNs were used as forward primers for the next-step polymerase chain reaction(PCR) to generate the final CMC-g-DNA hybrid copolymer. The infrared spectrum detection proved that the side carboxyl groups of the CMC were substituted very well by NHS and the efficiency was higher at acid condition than neutral. The obtained CMC-g-DNA copolymers were characterized by agarose gel electrophoresis and polyacrylamide gel electrophoresis, respectively. And the results showed that DNA was grafted on CMC successfully. An interesting finding is that CMC-g-DNA moved faster than control DNA in agarose gel electrophoresis, while it migrated slower than control polyacrylamide gel electrophoresis.

    High-capacity Polyvinyltetrazole-grafted Chelating Resin for Adsorption of Heavy Metal Ions
    CHEN Youning, GAO Li, HE Maofang, WEI Yinmao
    2014, 35(7):  1596-1602.  doi:10.7503/cjcu20140029
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    A novel polyvinyltetrazole-grafted chelating resin was prepared by grafting poly(acrylonitrile) onto the chloromethylated polystyrene beads via surface-initiated atom transfer radical polymerization(SI-ATRP), and followed by the reaction of cyano-tetrazole conversion under microwave assistance. The structure of the resin was characterized by Fourier transform infrared spectroscopy and elemental analysis, and the adsorption properties were evaluated with Pb(Ⅱ), Ni(Ⅱ) and Cd(Ⅱ). It was found that an increase in the polymerization time leads to the increases in grafting degree of acrylonitrile, the binding amount of tetrazoles and adsorption capacities of Pb(Ⅱ), Ni(Ⅱ), and Cd(Ⅱ). The results suggested that the polymerization of acrylonitrile on the resin surface was a controllable living polymerization, and the binding amount of tetrazoles on the resin surface and adsorption capacity of the resins could be adjusted by the polymerization time. The adsorption of three metal ions was mainly regarded as chemical adsorption based on the coordinating effect by analyzing the relationship between adsorption capacity with the solution pH, adsorption isotherm and adsorption kinetics. At the polymerization time of 10 h, the maximum sorption capacities of Pb(Ⅱ), Ni(Ⅱ) and Cd(Ⅱ) were 1.57, 1.68 and 1.92 mmol/g, respectively. Ten adsorption-desorption cycles demonstrated that the resin possessed high recycling efficiency and stability and was suitable for efficient removal of metal ions from aqueous solution.

    Preparation of Micro-spheres Co-carried Anti-tumor Drug and Sensitizer(5-Fu-COS/SeNP) and Their Inhibiting Tumorous Cellular Growths Activity
    TONG Chunyi, TANG Fengxia, LIU Bin, LIAO Hongdong, LIU Xuanming
    2014, 35(7):  1603-1607.  doi:10.7503/cjcu20131141
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    5-Fu-COS/SeNP micro-spheres were prepared in two steps to study the antitumor drug load and auxiliary same effects as the drug carrier. First, the Fu-COS prodrug was synthesized with the broad-spectrum anti-tumor drug 5-fluorouracil(5-Fu) and chito-oligosaccharides(COS), then, Fu-COS was used as temples while 5-Fu-COS/SeNP was prepared by sol-gel method. 5-Fu-COS/SeNP was characterized by TEM, Zeta-sizer and IR, and its anti-tumor activity was detected by MTT method. The results showed that 5-Fu and Se were completely carried in 5-Fu-COS/SeNP, the size of 5-Fu-COS/SeNP was 433 nm, the drug-loading rate of 5-Fu and Se were (8.2±0.3)% and (7.96±0.34)%, respectively, and 5-Fu and nanose released slowly and had well inhibiting tumorous cellular growths activity. As time increases, release rate of the drug by Fu-COS/SeNP increased and the inhibition of cell enhanced. After 24 h, inhibition rate had exceeded the sum of 5-Fu and SeNP. After 48 h, the inhibition rate of Fu-COS/SeNP was less than the sum of the inhibition rate of 5-Fu and SeNP, but higher than that of 5-Fu or SeNP. These results indicated that the spheres have high drug loading efficiency and good drug release properties. This novel method to produce micro-spheres could expand the development of drug release research.

    Temperature/pH Dual-sensitive Fluorescence Nano-gel Based on Cellulose Through Self-assembly Assisted Polymerization
    LI Zhenzhen, ZHOU Shuyan, DOU Hongjing, SUN Kang
    2014, 35(7):  1608-1614.  doi:10.7503/cjcu20131103
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    Temperature/pH dual-sensitive fluorescence nanogels(FNGs) were synthesized through a self-assembly assisted(SAA) “one-step” method. A hydrophilic fluorescence monomer 5-acrylamide fluorescein(5-AAF) has been fabricated, on this basis, graft copolymerization of 5-AAF from the backbone of hydroxypropyl cellulose(HPC) was initiated using ceric ammonium nitrate(CAN), the self-assembly of 5-AAF graft chains induced by both hydrogen bond and the hydrophobic interaction of fluorescence group proceeded with the polymerization of 5-AAF. Furthermore, N,N'-methylenebisacrylamide(MBA) was applied as crosslinker. As a result, FNGs were synthesized efficiently and environment-friendly with stable temperature/pH sensitivity properties. The environment-sensitivity of resultant FNGs can be tuned by changing molecular weight of HPC, the existence of hydrophobic/hydrophilic group on FNGs as well as the hydrogen bond contributed to FNGs’ temperature-sensitivity. Moreover, FNGs displayed impressive pH-sensitivity under various pH values, the fluorescence intensity can be rapidly enhanced at neutral and alkalic environment, while it quenches at acidic environment. The influence of pH on fluorescence intensity can be reversed without any other recovery process. The cytotoxicity of FNG was preliminarily studied, the results revealed good biocompatibility of FNGs. The temperature/pH responsivity of the FNGs’ fluorescence are of great potential in biomedical detection, such as fluorescence labeling, or temperature/pH sensor for micro-environment.