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    10 December 2017, Volume 38 Issue 12
    Content
    Cover and Content of Chemical Journal of Chinese Universities Vol.38 No.12(2017)
    2017, 38(12):  0-0. 
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    Volume Contents of Chemical Journal of Chinese Universities to Vol.38(2017)
    2017, 38(12):  1-1. 
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    Articles: Inorganic Chemistry
    Tunable Upconversion Luminescence of Mn2+ Doping NaBiF4∶Yb/Er Particles
    SU Yue, LEI Pengpeng, FENG Jing, ZHANG Hongjie
    2017, 38(12):  2135-2143.  doi:10.7503/cjcu20170620
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    NaBiF4∶Yb/Er/Mn samples with different concentrations of Mn2+ were fabricated via the solvothermal method. Also, the morphology and crystal phase, the changes of upconversion luminescence(UCL) upon different doping amounts of Mn2+ were investigated. Meanwhile, the mechanism of energy transfer in NaBiF4∶Yb/Er/Mn was also discussed. The results indicate that, for NaBiF4∶Yb/Er, Mn2+ doping does not induce transition from hexagonal to cubic phase, but increases the size of the particles. Meanwhile, the energy transfer processes between Er3+ and Mn2+ can take place in NaBiF4 host, which eventually enhances the red emission to a certain degree. With the increasing of the concentration of Mn2+, the intensity ratio of red to green emission is also increased. In addition, the temperature-dependent UCL spectra of NaBiF4∶Yb/Er/Mn was investigated, and the intensity ratios of red to green emission and 520 nm green emission to 540 nm green emission are generally increased with elevated temperature.

    Controllable Preparation and Fluorescence Property of Conch-like Self-assembled Calcium Carbonate
    ZHAO Lina, CAO Yang
    2017, 38(12):  2144-2148.  doi:10.7503/cjcu20170344
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    Using liquid phase precipitation method, special conch-like calcium carbonate particles were prepared with bismuth nitrate as an additive at 60 ℃. The structure and performance of the resulting calcium carbonate were characterized by means of scanning electron microscopy(SEM), X-ray diffraction(XRD), thermogravimetric analysis(TGA) and atomic fluorescence spectroscopy(AFS). The results showed that the fluorescence of the conch-like calcium carbonate particles was enhanced obviously. Bi3+ played a significant controlling role in the nucleation process of calcium carbonate.

    Synthesis of Palladium Right Bipyramids with a Singly Twinned Structure
    SUN Changyong, LIN Liangbiao, XIE Xiaowei
    2017, 38(12):  2149-2155.  doi:10.7503/cjcu20170337
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    Through solution phase reduction route, palladium right bipyramid nanocrystals with a singly twinned structure were synthesized with Na2PdCl4 as a precursor, PVP as a stabilizer and reductant, I- as a plane-selective capping agent and coordination reagent, and NO3- as an etching agent in a hydrophilic system. When n(Na2PdCl4)∶n(PVP)∶n(KI)∶n(NaNO3)=1∶35∶10∶9 and pH=11, well-defined palladium right bipyramid nanocrystals with purity higher than 99% could be achieved. I- in the present reaction system affected the growth and transformation of crystal seed and the morphology of final product by changing reduction rate of Pd precursor, whereas the effect of I- on oxidative etching was not obvious at high pH value. The ratio of K+/Na+ considerably influenced the morphology of product, showing a cation effect, which was possibly attributed to higher reduction rate in the presence of Na+ than that in the presence of K+.

    One-step Synthesis of Activated Carbon from Molasses and Its Interfacial Adsorption Behavior
    GAO Ye, WANG Wei, PANG Liyun, CAO Liyuan, GUO Yupeng, ZHAO Chun
    2017, 38(12):  2156-2162.  doi:10.7503/cjcu20170221
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    The molasses-based activated carbon(AC) was prepared with Na2CO3 as activator by one-step chemical activation method. With the characterization of X-ray diffraction(XRD), scanning electron microscopy(SEM), N2 adsorption-desorption analysis and elemental analysis, the results showed that the activated carbon is graphitized carbon with specific surface area of 1023 m2/g. The removal capacity of molasses-based activated carbon on Pb(Ⅱ) in solution was studied, the results showed that the adsorption capacity of molasses-based activated carbon was higher than that of commercial activated carbon(CC). With the molasses-based activated carbon as adsorbent, the adsorption time was shorter and the mass of activated carbon were lower than those with commercial activated carbon as adsorbent. The adsorption kinetic fitted better to pesudo-second-order Langumir model, demonstrating a chemical adsorption of monolayer. The molasses-based activated carbon can be recycled and reused for Pb(Ⅱ) adsorption.

    Analytical Chemistry
    Preparation and Application of Novel Fluorescence Chemical Sensor for Determining Trace Levels of Picronitric Acid Based on Water Soluble Conjugated Polymer
    LIU Jilin, MI Hongyu, GUAN Mingming, HUAN Yanfu, FEI Qiang, ZHANG Zhiquan, FENG Guodong
    2017, 38(12):  2163-2168.  doi:10.7503/cjcu20170272
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    A water soluble conjugated polymer{poly[2,5-bis(sodium 4-oxybutyrate)-1,4-phenylethyny-lene-alt-1,4-phenyleneethynylene], PPE-OBS}, was synthesized for the detection of picronitric acid(PA). PPE-OBS was characterized by means of mass spectrometry, NMR spectroscopy, infrared spectroscopy(IR), and so on. The experiment conditions and detection performance of PPE-OBS were systematically studied. The results show that the fluorescent quenching of PPE-OBS is the most efficient when the reaction time between PPE-OBS and PA is 20 min in the boric acid-sodium hydroxide buffer solution(pH=9.5). The results demonstrate that PPE-OBS as a sensor for PA has a good linear range from 1.0 to 60 μmol/L with the calculated limit of detection(LOD) to be 0.831 μmol/L. Meanwhile, PPE-OBS paper was applied to rapidly detecting PA in environmental water samples.

    Cu2+ Modified Gold Nanoclusters for Fluorescence Turn-on Detection of Dopamine
    YU Xijuan, HAN Lulu, HUN Xu
    2017, 38(12):  2169-2175.  doi:10.7503/cjcu20170251
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    One-step hydrothermal method was used for the preparation of water-soluble gold nanoclusters(AuNCs) with strong fluorescence using 11-mercaptoundecanoic acid(11-MUA) as reducing agent and protective agent. A turn-on fluorescent probe based on Cu2+ modified AuNCs@11-MUA was developed for the detection of DA with high sensitivity and selectivity. After Cu2+ ions were added into AuNCs@11-MUA solution, the fluorescence of AuNCs@11-MUA was quenched, and the fluorescence signal of the system was in the “off” state. In the presence of DA, a more stable complex than the AuNCs@11-MUA-Cu2+ complex was formed due to DA and Cu2+ have a stronger binding force, which resulted in the departure of Cu2+ from the surface of the AuNCs@11-MUA, and the fluorescence signal of the system was “open”. The fluorescence recovery degree of the AuNCs@11-MUA probe showed a good linear relationship with the concentration of DA from 2.0×10-7 mol/L to 5.0×10-5 mol/L. The limit of detection was estimated to be 8.0×10-8 mol/L(S/N=3). The present method was applied for the detection of DA in human serum and urine. Recoveries were found to be in the range of 93.2%—97.3%, and the result of statistical calculation shows that relative standard deviations(RSDs) were lower than 4.08%. The results indicate that present method can be applied for the detection of DA in the human body.

    Logic and Reversible Dual DNA Detection Based on the Assembly of Graphene Oxide and DNA-templated Quantum Dots
    SHEN Xiaoqin, LI Zhi, WANG Ganglin, WANG Li, SUN Quanhong, LUO Xucheng, MA Nan
    2017, 38(12):  2176-2184.  doi:10.7503/cjcu20170246
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    We prepared water-soluble monolayer graphene oxide(GO) and DNA-templated CdTe quantum dots(P1), which were further assembled via π-π stacking interaction to generate nano-biosensors for the logical detection of dual DNA molecules with high selectivity. Moreover, reversible cyclic dual DNA detection is realized by changing DNA sequences, which enables regeneration of the biosensors. A variety of instruments were used to characterize biosensor preparation and detection process including atomic force microscopy(AFM), transmission electron microscopy(TEM), electrophoresis, fluorescence spectroscopy and so on. The prepared nano-biosensor holds great promise for nucleic acid detection.

    Organic Chemistry
    Transformation of Total Notoginsenosides by Recombinant Endocellulase Fpendo5A
    LI Nan, ZHAO Huanxi, LI Jing, WANG Nan, YU Bohao, YUE Hao, YU Shanshan
    2017, 38(12):  2185-2192.  doi:10.7503/cjcu20170314
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    A novel endocellulase(Fpendo5A) was cloned from Fervidobacterium pennivorans DSM9078. After being overexpressed and purified from Escherichia coli, the enzymatic properties of Fpendo5A were investigated. Also, rapid resolution liquid chromatography coupled with quadruple-time-of-flight mass spectrometry(RRLC/Q-TOF-MS) was performed to investigate the biotransformation process of the total notoginsenosides by Fpendo5A. Fpendo5A exhibited an optimal activity at 80 ℃ and pH=5.5 and showed the highest activity for carboxymethyl cellulose(CMC), which indicated that Fpendo5A was a thermophilic and acidophi-lic endocellulase. Also, Fpendo5A showed high biotransformation ability for ginsenoside Ra1, Rb1, Rc, Rd and Rg3, which are the main components in the total notoginsenosides. Ra1, Rb1, Rc, Rd and Rg3 were converted to Rb2, Gyp ⅩⅦ, CMC1, F2 and Rh2, respectively by Fpendo5A.

    Fucoidan Degradation and Preparation of Fuco-oligosaccharides from Saccharina japonica
    GENG Lihua, JIN Weihua, WANG Jing, ZHANG Quanbin
    2017, 38(12):  2193-2197.  doi:10.7503/cjcu20170232
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    The sulfated fuco-oligosaccharides were prepared via acid hydrolysis degradation of crude fucoidan extracted from Saccharina japonica. Through the optimization of degradation and precipitation conditions, the hydrolysis and sedimentation law of fucoidan were studied. Physicochemical analysis showed that the supernatant was heterozygous sulfated fuco-oligosaccharide(fucose>55%). Four fractions of fucose based low polyme-rization degree of oligosaccharides were purified by Bio-Gel P4 low-pressure permeation chromatography, and the fucose content of the fractions was up to 90% according to monosaccharide composition analysis and electrospray ionization mass spectrometry(ESI-MS) analysis. Thus, the fractions were series of low-polymerized sulfated fuco-oligosaccharide/fucose, and the major fractions could be expressed with the formula of Fuc1~3S1~3, Fuc1~2S1~2, Fuc1~2S, and FucGlcAS.

    Imidazolium-bis(salicylato)borate Ionic Liquids as Lubricant Additives: the Effect of Alkyl Chain Lengths on the Tribological Performance
    SUN Liwen, ZHANG Yunxiao, CAI Tao, SHANG Wangji, LIU Dan, TONG Dingyi, LIU Shenggao
    2017, 38(12):  2198-2205.  doi:10.7503/cjcu20170205
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    Seven environmental-friendly ionic liquids containing chelated organoborate anions having different alkyl chain lengths were synthesized and then evaluated as potential lubricant additives. The 1H NMR, TGA and DSC were employed to characterized the structure and thermal properties of synthesized ionic liquids. The tribo-performacne were systematically studied by four-ball machine and SEM-EDX as well. The synthesized ionic liquids were found to be quite stable at room temperature and showed remarkable improvement in the anti-wear properties of the poly(ethylene) glycol(PEG200) lube base. The results showed that ionic liquids as additives significantly reduced the wear of PEG200, and particularly the variation in substituted alkyl chain length on the imidazolium ring monitored the degree of reduction in wear. C6ImC8BScB shows the excellent friction reducing properties among all the synthesized ionic liquids, the coefficient of wear scar diameter lubricated by PEG under 392 N corresponding reduced with mass fraction of 27.49%.

    Physical Chemistry
    Preparation,Characterization and Gas Sensing Properties of Sn Doped MoO3
    GAO Haiyan, WANG Jingyi, ZHAO Yongnan, CHEN Kunfeng, XUE Dongfeng
    2017, 38(12):  2206-2212.  doi:10.7503/cjcu20170470
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    Sn-doped MoO3 were synthesized by a hydrothermal method, using ammonium paramolybdate and tin tetrachloride as raw materials. The structure, morphology and pore texture of the samples were characterized by means of X-ray diffraction(XRD), scanning electron microscope(SEM) and Brunauer-Emmett-Teller(BET). The gas sensing properties of ethanol, dichloromethane, methanol, formaldehyde, formic acid, carbon tetrachloride, ammonia and acetone were tested. The results show that Sn doping does not affect the structure of MoO3 and the best heating temperature is 290 ℃. After Sn doping, the sensitivity is better than the pure MoO3, and the response time is shorter. MoO3 doped with 5%(molar ratio) Sn shows the best gas sensing properties, with a gas sensitivity of 19.64 and a rapid response time of 1.1 s in 500 mg/m3 of ethanol.

    Theoretical Study on the Anti-CO Poisoning Performance of PtFe Doped Graphene
    TONG Yongchun, WANG Qingyun, WANG Yongcheng, TANG Lin
    2017, 38(12):  2213-2219.  doi:10.7503/cjcu20170415
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    The anti-CO poisoning ability of Pt, Fe and PtFe binary metal catalysts with single-vacancy defect(SV) graphene as carrier was studied based on the density functional theory(DFT). For the single metal atoms Pt and Fe, Fe is more easily adsorbed on SV graphene. For PtFe binary metal catalyst, SV graphene has a tendency to further strengthen its stability. The anti-CO poisoning ability of PtFe-6 structure is better than Pt-SV, and is more close to the anti-CO poisoning ability of Fe-SV. PtFe-6 is also the most stable among all binary metal catalysts, close to the Fe adsorption on the SV graphene. Therefore, the anti-CO poisoning ability of anodic Pt catalyst in DMFC can be improved by adding non-noble metal Fe in Pt, and its catalytic activity can also be enhanced.

    Studies of Raman Spectra and Theoretical Calculation of MnCl2/DMSO Solution
    WU Xiaojing, LIU Azuan
    2017, 38(12):  2220-2225.  doi:10.7503/cjcu20170390
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    The ion solvation of MnCl2/DMSO solutions was investigated by Raman spectra in different concentrations and temperatures. The results indicated that Mn2+ coordinated with DMSO molecules in the form of ions in the solutions, and the interaction gradually strengthened with the increase of concentrations between 0—0.8 mol/L. With the solvation of Mn2+ and DMSO molecules interaction increasing, S=O double peaks moved to low wave number, so S=O double bond weakened; C—S stretching vibration peak moved to high wave number, so C—S bond strengthened. Rising temperature, S=O double bond and C—S bond vibration peaks moved to the opposite direction, and the solvation effects gradually weaken. Above 56 ℃, monomer DMSO molecules rapidly increasing, DMSO molecules in the solvation sphere of the manganese cation rapidly reducing, dimer DMSO molecules slowly reducing, that illustrated that temperature had a greater influence on solvation effects than the association of solvent itself. Moreover the optimized possible solvation configuration [Mn(DMSO)n]2+, thermodynamic properties, and the theory of Raman spectra were calculated by density functional theory. The solvation of Mn2+ and DMSO molecules was confirmed by theory, which resulted in stretching of S=O bond and the contraction of C—S bond, consisting with the results of the experimental spectrum.

    In-situ Photocatalytic Process of Rhodamine B over g-C3N4@Ag3PO4 Nanocomposites Based on Photomicrocalorimeter-fluorescence Spectrometry
    WAN Ting, LI Xingxing, HUANG Zaiyin, QIU Jiangyuan, ZUO Chen, TAN Xuecai
    2017, 38(12):  2226-2230.  doi:10.7503/cjcu20170371
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    A photomicrocalorimeter-fluorescence spectrometer was applied to obtain in-situ thermodynamics, kinetics and 3D fluorescence spectra of Rhodamine B photocatalysis over g-C3N4@Ag3PO4 nanocomposites. And its mechanism was investigated by coupling the thermodynamics and its spectroscopic information. Consequently, the whole process underwent an initial endothermic reaction and a subsequent exothermic stage, and finally maintained a stable exothermic platform. The intensity of fluorescence emission peak of Rhodamine B over g-C3N4@Ag3PO4 decreased sharply within the illumination of 10 min, its degradation rate reached 92.9%, which was 2.06 times that over g-C3N4. Subsequently, the photodegradation of the ring and intermediates without fluorescent chromophores were dominated, which maintained a stable exothermic rate of -(0.226±0.0916) mJ/s with a pseudo-zero order process. This process was the rate-determining step. Therefore, Rhodamine B photocatalysis was a pseudo-zero-order process rather than a first order process.

    Molecular Dynamics Simulations on Crystal Morphology of N-Guanylurea-dinitramide
    LIU Ning, ZHOU Cheng, SHU Yuanjie, WANG Bozhou, WANG Wenliang
    2017, 38(12):  2231-2237.  doi:10.7503/cjcu20170363
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    The crystal morphologies of N-guanylurea-dinitramide(FOX-12) under solvent condition were investigated by molecular dynamics simulation with canonical(NVT) ensemble. The FOX-12 surface-solvent molecule adsorption model was constructed to simulate dynamical equilibrium configuration. By calculating the binding energies of solvent and crystal surfaces, the attachment energies in vacuum were modified and the crystal shapes in different solutions were obtained. The FOX-12 crystals were cultivated in H2O and H2O/MeOH by natural cooling and characterized by scanning electron microscopy. The results show that the morphologically dominant faces of FOX-12 in vacuum are (110), (200), (201), (011), (002) and (111); the (110) and (011) faces are found to be the morphologically important growth faces in H2O; the (200) and (011) faces are found to be the morphologically important growth faces in H2O/MeOH; the predicted crystal morphologies of FOX-12 were in agreement with the experimental results. Furthermore, the radial distribution function(RDF) analyses between H2O molecules and (110) face of FOX-12 were performed to explore the solvent-crystal interactions.

    Effect of Bovine Serum Albumin on the Structure of DSPE Monolayer
    XU Guoqing, HAO Changchun, HE Jianzhen, ZHANG Lei, SUN Runguang
    2017, 38(12):  2238-2247.  doi:10.7503/cjcu20170359
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    The effect of bovine serum albumin(BSA) on the 1,2-distearoyl-sn-glycero-3-phosphoethanolamine(DSPE) monolayer at air-water interface was investigated by Langmuir-blodgett(LB) technique and atomic force microscopy(AFM) observation. The surface pressure-mean molecular area(π-A) isotherms, adsorption curves and compression-expansion cycle curves of DSPE monolayers were obtained by changing the pH values and the concentration of BSA. The results indicated that the presence of BSA in the subphase had a great influence on the compressibility, stability and phase transition behavior of DSPE monolayers. The adsorption kinetic indicated that BSA was adsorbed onto DSPE monolayers and a threshold value existed, which was affected by the pH value. Analysis of experimental data showed that most hydrophobic residues of BSA were exposed to water at pH=3, so the interaction between BSA and DSPE was strongest. However, the interaction was the weakest at pH=7 because less hydrophobic residues were exposed to water. The change of surface morphology structure observed by AFM was consistent with the results obtained from curves. This study provides an important experimental basis and theoretical basis for understanding the interaction mechanism between serum proteins and phospholipid molecules.

    Selective Oxidation of Cyclopentene to Glutaraldehyde Catalyzed by Heteropolyphosphatotungstate Ionic Liquids
    ZHANG Jinshuai, YU Fengli, TAO Renqing, XIE Congxia, YUAN Bing, YU Shitao
    2017, 38(12):  2248-2254.  doi:10.7503/cjcu20170355
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    With H2O2 as oxidant, a series of heteropolyphosphatotungstate ionic liquids was used to catalyze the selective oxidation of cyclopentene(CPE) to prepare glutaraldehyde(GA). Among these catalysts, [π-C5H5NC16H33]3PW4O16 exhibited the best catalytic activity. PW4O163- easily combined with H2O2 to form W—O—O—W. Using [π-C5H5NC16H33]3PW4O16 as catalyst, the effects of the amount of catalyst, molar ratio of H2O2 to CPE, type and dosage of solvent, reaction temperature and reaction time on the catalytic behavior were investigated and discussed, respectively. The results show the best reaction conditions as follows: 5 mL of ethyl acetate, n(Cat.)∶n(H2O2)∶n(CPE)=0.03∶50∶33, 35 ℃, 18 h. The conversion of cyclopentene could reach 100%, and the yield of glutaraldehyde was 87%. After the reaction, the catalyst could automatically precipitate from the reaction liquid. After the upper liquid was poured out, the remaining catalyst could be directly reused by the addition of fresh reactants. Under the optimal reaction conditions, the recycling efficiency of the catalyst [π-C5H5NC16H33]3PW4O16 was investigated. Because the structure of the catalyst didn’t change before and after reaction by the analysis of FTIR spectra, [π-C5H5NC16H33]3PW4O16 has exhibited a good recyclability. After 7 recycles, the yield of glutaraldehyde was still above 80%.

    Graphene Supported Nickel Catalyst for Methanation of Carbon Dioxide
    ZHANG Rongbin, TONG Sai, YANG Jinmei, TANG Xiannong, HUANG Chuanqing, WANG Xuewen, FENG Gang, CAI Jianxin
    2017, 38(12):  2255-2261.  doi:10.7503/cjcu20170348
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    Graphene oxide(GO) was prepared from purified natural graphite via the modified Hummers method, and hydrazine hydrate reduced graphene oxide supported nickel catalysts were prepared via impregnation method. The influence of different supports of Ni-based catalysts for the carbon dioxide methanation reaction was investigated. Using reduced graphene oxide(RGO), carbon nanotubes(CNTs) and activated carbon(AC) as supports, nickel catalysts with different morphologies were formed. The prepared samples were characterized by FTIR, BET, H2-TPR, XRD and TEM techniques and applied in carbon dioxide methanation. The results reveal that Ni/RGO has a relative large specific surface area(316 m2/g). The particle size of nickel on Ni/RGO(5.3 nm) is smaller than that on Ni/CNTs(8.9 nm) and Ni/AC(11.6 nm). Ni/RGO shows better catalytic activity and selectivity of carbon dioxide methanation reaction than that on Ni/CNTs and Ni/AC. Ni/RGO catalyst has a remarkable stability.

    Depletion Potential and Adsorption Stability of a Colloidal Particle in Confined Solvent Mixture
    KANG Yanshuang, SUN Zongli, TAN Shanshan
    2017, 38(12):  2262-2270.  doi:10.7503/cjcu20170331
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    Based on density functional theory and Yvon-Born-Green equation, the expression for depletion potential was derived. The depletion potential and adsorption stability were calculated and investigated via density functional theory for the colloidal particles immersed in the solvent mixture, which was confined by a single wall and in slit pore. The results showed that the volume fraction and the size ratio of the solvents influence significantly the depletion potential in its strength, range and oscillation period. Moreover, the adsorption stability of the colloidal particle at the wall related closely to the volume fraction and size ratio of the solvents. In addition, for the colloidal suspension confined in slit pore, the depletion potential-well of a colloidal particle might show oscillation as the size ratio and the pore width were modulated.

    Membrane Structure Alteration of DOPC Liposome Induced by Interaction with Gene Carrier Polyethyleneimine
    WEI Yanshan, WEI Bangzhi, HUANG Aimin, MA Lin
    2017, 38(12):  2271-2279.  doi:10.7503/cjcu20170273
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    To get a better understanding on the molecular basis of the cytotoxicity of PEI which has been considered as “golden standard” for polymeric gene delivery carriers. Dynamic light scattering, fluorescence spectra, zeta-potential measurement and isothermal titration calorimetry were conducted to reveal the mechanism of interaction between PEIs(average molecular weight of 25000, 10000 and 1800) and 1,2-dioleoyl-sn-glycero-3-phosphatidylcholine(DOPC) liposome. The influence on the polarity of microenvironment and the permeability of liposome bilayer were also investigated. The result showed that PEI bound to DOPC vesicles via hydrogen bond or van Waals interactions between the amide groups and the phosphorylcholine heads. The complex formation with PEI induced aggregation and increase in zeta potential of liposomes at low PEI concentration up to 0.075 mg/mL. A further increase in PEI concentration made little change on the surface potential, however reduced the aggregation of the vesicle due to the repulsion between the adsorbed PEI chains. PEI binding decreased the packing density of hydrocarbon chain of lipid molecules and the hydrophobicity in the bilayer membrane, and thus resulted in an enhanced permeability of calcein and quercetin through the membrane. The polymer size played an important role in PEI-DOPC liposome interaction. PEI with higher molecular weight was more favorable to interact with DOPC and more efficient to perturb the structural properties of the membrane.

    Molten Salt-assisted Microwave Synthesis and Nitrogen Photofixation Ability of Nickel Doped Graphitic Carbon Nitride
    QU Xiaoyu, HU Shaozheng, LI Ping, WANG Fei, ZHAO Yanfeng, WANG Qiong
    2017, 38(12):  2280-2288.  doi:10.7503/cjcu20170223
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    In this work, nickel doped g-C3N4 was synthesized via a novel molten salt-assisted microwave process. X-ray diffraction(XRD), N2 adsorption, UV-Vis spectroscopy, scanning electron microscopy(SEM), temperature-programmed desorption(TPD), X-ray electron spectroscopy(XPS), photoluminescence spectroscopy(PL) and electrochemical impedance spectroscopy(EIS) were used to characterize the prepared catalysts. The results show that the molten salt-assisted microwave process changes the morphology of prepared catalyst from layered structure to nanoparticles. These nanoparticles are closely packed with each other to form many secondary pores, which increases the catalyst surface area. Besides, due to that the raw materials are wrapped by the liquid-phase molten salt during the microwave process and can not be in contact with oxygen, Ni is not only present as inactive oxide but inserts at the interstitial position to form active Ni(Ⅰ)—N bonds. This Ni(Ⅰ)—N active sites can activate N2 molecules, promote separation rate of electrons and holes, and accelerate interfacial charge transfer from catalysts to N2 molecules, thus significantly improving the nitrogen photofixation ability.

    Influences of Freezing on the Reduction of Cr(Ⅵ) by Typical Components of Dissolved Organic Matter
    ZHONG Yubo, KANG Chunli, WANG Yueqi, XU Xiaolei, BAO Siqi, XUE Honghai, TIAN Tao
    2017, 38(12):  2289-2295.  doi:10.7503/cjcu20170191
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    The influences of freezing on the reduction of Cr(Ⅵ) by four typical components of dissolved organic matter(DOM), namely oxalic acid, tartaric acid, malic acid and citric acid, were investigated. The results show that under the condition of a low concentration in the experiments, Cr(Ⅵ) in the aqueous solution cannot be reduced by those four organic acids. However, in the ice, the four organic acids all facilitate to remove Cr(Ⅵ). Moreover, the removing effects gradually strengthens with the increasing concentration of organic acids. And the effects of these four organic acids rank as oxalic acid>tartaric acid>malic acid>citric acid. The concentration of inorganic salts and inorganic acid can inhibit the reduction of Cr(Ⅵ) by changing the thickness of liquid-like layers in the ice surface, but the inhibiting effect is independent of the kinds of inorganic salts. It is the initial pH of the solution and the structure of the organic acid that greatly influence the reduction of Cr(Ⅵ). Upon the experiment condition, the concentration factor of the freeze-concentration effect can reach 103 at least, which apparently facilitates the oxalic acid to remove Cr(Ⅵ) in the ice.

    CuO Catalyst Supported on CeO2 Prepared by Oxalate Thermal Decomposition Method for Preferential Oxidation of CO
    WANG Cheng, GUO Lihong, LI Xingang, MA Kui, DING Tong, WANG Xinlei, CHENG Qingpeng, TIAN Ye
    2017, 38(12):  2296-2305.  doi:10.7503/cjcu20170181
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    A series of CuO/CeO2 catalysts with different CuO loadings was prepared via oxalate thermal decomposition-impregnation method for the CO preferential oxidation(PROX) reaction. The catalyst with 10% CuO loading has the best activity, with the lowest and the widest CO full conversion temperature window of 96—160 ℃, and 100% selectivity to CO2 below 131℃. The results indicate that the Cu-Ce solid solution is formed when a small amount of CuO is loaded. However, the increased CuO loading will result in the aggregation of CuO on the surface of CeO2, which is unfavorable to form the solid solution. For the CuO/CeO2 catalysts, the formation of Cu-Ce solid solution can inevitably generate surface oxygen vacancy and Ce3+, which can react with the Cu2+ to produce Cu+ through the balance of Ce3++Cu2+ \(\rightleftharpoons\) ? Ce4++Cu+. As the Cu+ is the active center for the CO PROX, the increased surface Ce3+ content and the strengthened interaction between CuO and CeO2 can enhance the CO PROX activity of the catalyst. Compared with the CuO/CeO2 catalysts prepared by precipitation-impregnation method, the catalysts prepared by oxalate thermal decomposition-impregnation method have the higher surface Ce3+ content and stronger interaction between Cu and Ce, resulting in the better CO PROX activity.

    Preparation and Performance in Supercapacitor of Three-dimensional Functionalized Graphene/polyaniline Freestanding Electrode Materials
    LI Xuehang, YU Huitao, WANG Weiren, BULIN Chaoke, XIN Guoxiang, ZHANG Bangwen
    2017, 38(12):  2306-2312.  doi:10.7503/cjcu20170110
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    Three dimensional graphene(3D-G) was prepared by hydrothermal method, in which graphene layer increased the electron transfer within the channels. Octadecylamine(ODA) functionalized graphene/polyaniline(G-ODA/PANI) was prepared by the modification of reduced graphene materials with ODA and in situ polymerization of aniline on the surface og G-ODA. Structure, electrochemical properties and the specific capacitance contribution of the materials were analyzed. The results showed that the contribution of capacitor electrode material was originated from the pseudocapacitive properties of polyaniline. The specific capacitance of G-ODA/PANI electrode reached 1080 F/g at current density of 1 A/g, 2.57 times as high as that of graphene/polyaniline(G/PANI) electrode material. It also had a great increase in cycle stability, and the capacity retention rate was 90.8% after 10000 cycle times, increased by 9.6% compared with G/PANI.

    Preparation and Photocatalytic Properties of Pr-doped Bi2MoO6/TiO2 Composite Nanofibers Under Visible Light Irradiation
    LI Yuejun, CAO Tieping, MEI Zemin, XI Xiaotian, WANG Xia
    2017, 38(12):  2313-2319.  doi:10.7503/cjcu20170097
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    Praseodymium-doped Bi2MoO6/TiO2 composite nonafibers were prepared via solvothermal growth of Bi2MoO6 nanostructures on the substance of the electrospun anatase TiO2 nanofibers. The phase composition, morphology, microstructure and optical properties of the samples were characterized by X-ray diffraction scanning electron microscopy, energy dispersive X-ray spectroscopy, high-resolution transmission electron microscopy, UV-Vis diffuse reflectance spectroscopy and photoluminescence spectroscopy. The photocatalytic activity of the samples were evaluated by photodegradation of methyl orange solution under visible light. The results showed that the Pr3+ was incorporated into the Bi2MoO6 crystal lattice to form the donor level, which facilitated the activation of the photocatalyst by visible light, retarded the recombination of photo-induced electrons-holes, and inhibited the leaching of dopants, leading to an enhanced activity and good recycling stability. The 3%(molar faction) Pr-doped Bi2MoO6/TiO2 photocatalyst exhibited the best activity, with a MO degradation rate of 93.8% after visible light irradiation for 180 min. The Pr-doped Bi2MoO6/TiO2 composite nanofibers exhibited superior photocatalytic activity compared to the Bi2MoO6/TiO2 composite nanofibers.

    Methanol Electrocatalytic Oxidation on Pt/Poly(o-toluidine) Film/Activated Carbon Doped Graphite Carbon Paste Electrode
    ZHANG Yuanyuan, LI Fenpei, LIU Xiangqing, CHEN Haiyan, LUO Ying, JING Lihong, LU Jiaxing, ZHANG Guirong
    2017, 38(12):  2320-2327.  doi:10.7503/cjcu20170093
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    Various liquid oil-bound carbon paste electrodes were prepared from the mixtures of graphite powders and paraffin(CPE), multi-walled carbon nanotubes and graphite powders and paraffin(MWCNT-CPE), graphene and graphite powders and paraffin(GRA-CPE), activated capacitors carbon and graphite powders and paraffin(YEC-CPE), activated batteries carbon and graphite powders and paraffin(YBC-CPE), respectively. Poly(o-toluidine)(POT) film was prepared by constant potential deposition at 0.85 V(vs. Ag|AgCl) in monomer solution at the surface of CPE and YBC-CPE(14%)(14% refers to the mass fraction of YBC in the carbon mixture materials) with various film growth charges. Platinum nanoparticles were successfully electrodeposited on Y-CPE(Y refers to the various carbon materials mentioned above except graphite powders), POT/CPE, POT/YBC-CPE(14%) at a fixed potential of -0.10 V(vs. Ag|AgCl) in 0.5 mol/L H2SO4 solution containing 3.0 mmol/L H2PtCl6. In order to learn about the instantaneous or progressive nucleation process of platinum on composite electrodes, non-dimensional plots of (I/Im)2 vs. t/tm of the experimental were compared with theory through the expressions. The morphologies of platinum nanoparticles were char-acterized by scanning electron microscopy(SEM). The SEM images reveal that the presence of YBC and POT influences the size of platinum nanoparticle. The electrocatalytic activities of as-formed Pt/CPE, Pt/POT/CPE, Pt/YBC-CPE and Pt/POT/YBC-CPE(14%) towards the electrooxidation of methanol were evaluated by cyclic voltammetry(CV). The experimental results indicate that compared with other POT/Y-CPE, Pt/POT/YBC-CPE(14%) has the best electrocatalytic activity towards methanol oxidation in an acidic medium.

    Polymer Chemistry
    Fabrication of Hollow TiO2 Spheres and Effect on Properties of Polyacrylate Film
    BAO Yan, GAO Min, DONG Yufei, KANG Qiaoling, GAO Zhipeng, WU Guodong, LI Yan
    2017, 38(12):  2328-2336.  doi:10.7503/cjcu20170258
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    Hollow TiO2 spheres were prepared using cationic polystyrene microspheres as templates, tetrabutyl titanate as titanium source and ammonia as catalyst. The morphology and structure were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and Brunauer-Emmett-Teller analysis. The influence of template size, titanium source and catalyst dosage on the morphology of hollow TiO2 spheres were studied. Then, the hollow TiO2 spheres were introduced into polyacrylate emulsion by physical blending method. The thermal insulation, UV-shielding and mechanical performance of composite films were investigated. As a result, the anatase phase hollow TiO2 spheres were obtained. The hollow size, thickness and compactness of the shell of hollow TiO2 spheres were influenced by the template size, titanium source and catalyst dosage. Hollow TiO2 spheres as filler can enhance the thermal insulation, UV-shielding and mechanical performance of polyacrylate film, significantly. At the same time, it was proved that the hollow TiO2 spheres prepared with different size templates have effects on the performance of the composite films. In which, the properties of the composite film containing the hollow TiO2 spheres prepared with template of 140 nm was optimal. The reflectivity was improved about 62.2%, the thermal conductivity was decreased by 17.71%, and the ultraviolet transmittance was almost zero under 390 nm wavelength.

    Synthesis of a Phosphorus/Nitrogen/Sulphur Containing Phosphazene Micro-Nanotube and Its Flame Retardancy on Epoxy Nanocomposite
    ZHAO Shishi, HE Meng, SONG Wenyao, ZHANG Chong, XU Jianzhong, MA Haiyun
    2017, 38(12):  2337-2343.  doi:10.7503/cjcu20170227
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    A highly cross-linked poly(cyclotriphosphazene-co-4,4'-sulfonyldiphenol)(PZS) nanotubes were synthesized via an in situ template method using cyclotriphosphazene(HCCP) and 4,4'-sulfonyldiphenol(BPS) as raw materials. PZS micro-nanotubes were applied on epoxy resin(EP) and the flame retarded mechanism was studied. The PZS micro-nanotubes were characterized by SEM, TEM, EDS and element Mapping. The thermalstability of PZS/EP nanocomposites were explored through TG, as compared to that of EP, and the flammability was investigated by microscale combustion calorimeter(MCC) and limit oxygen index(LOI) tests. The TGA results showed that a decreased initial degradation temperature, the residue chars were greatly improved. The flame retardancy was significantly enhanced by the addition of PZS micro-nanotubes. The residue char was improved 46% and the heat release rate was reduced 40% under addition of PZS micro-nanotubes(5%). The LOI value was also improved from 26.0% to 30.6%. The mechanical strength was also improved by the addition of PZS micro-nanotubes. The improvement of flame retardancy can be ascribed to the good dispersion and the formation of graphene-like structure during combustion of PZS/EP nanocomposites. In conclusion, PZS micro-nanotube is a kind of excellent flame retardant with potential application value.

    Fabrication of Cellulose/Nano Lamellar ZnO Composite Antibacterial Fibers Using Ionic Liquid
    FU Ranran, JI Xiujie, LIU Chao, REN Yanfei, WANG Gang, CHENG Bowen
    2017, 38(12):  2344-2351.  doi:10.7503/cjcu20170206
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    Lamellar superstructured ZnO was synthesized via an improved template method in which sodium dodecyl sulfonate(SDS), Zn(NO3)2·6H2O and NaOH were used as supramolecular template, Zn source and precipitant, respectively. Cellulose/nano lamellar ZnO composite fibers with ZnO 3%, 5%, 7%, 9% loading were processed from wood pulp and nano lamellar ZnO in the solution of 1-allyl-3-methylimidazolium chloride([Amim]Cl) by blending method via dry-jet wet spinning. The lamellar ZnO and its nanocomposites with cellulose were examined by X-ray powder diffraction(XRD), X-ray photoelectron spectroscopy(XPS), transmission electron microscope(TEM), field emission scanning electron microscopy(FESEM), and thermogravimetric analysis(TG). The influence of ZnO on the rheological property of composite systems was discussed. Besides, the strength and antibacterial activity of the composite fibers were tested. The results indicated that the as-synthesized ZnO presented a pure and well crystallized hexagonal wurtzite phase ZnO, as well as a periodic of 3.58 nm lamellar superstructure. Due to the addition of nano lamellar ZnO, the cellulose/ZnO nanocompo-sites exhibit better thermal stability and mechanical properties than original cellulose. Furthermore, antimicrobial assessment show that the composite fiber possess excellent antibacterial activities against S. aureus and E. coli. ZnO was exfoliated by cellulose chains. The ZnO platelets were homogeneously dispersed in cellulose/ZnO compounds. Besides, the rheology results showed that the presence of nano ZnO increased the viscosity of cellulose solution. When the ZnO content was 5% or above, in the whole frequency range, elasticity modulus was greater than the loss modulus, which inferred that nanoparticles could suspend steadily.

    Fabrication and Microwave Absorption Performances of EG-PANI-Fe3O4 Composites
    ZHANG Long, HOU Jieqiong, QIU Hu, DUAN Wenjing, WANG Xiaorui, WAN Xiaona, DU Xueyan
    2017, 38(12):  2352-2360.  doi:10.7503/cjcu20170188
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    Expanded graphite/polyaniline(EG/PANI) composites were synthesized by in-situ polymerization, and EG/PANI/Fe3O4 composites were obtained by adsorbing Fe3O4 nanoparticles on the surface of EG/PANI composites. The surface morphologies, phase structures and microwave absorption properties were characterized by scanning electron microscopy(SEM), X-ray diffraction(XRD), Fourier transform infrared(FTIR), and vector network analyzer(VNA). The results showed that when the HCl concentration was 0.05 mol/L, the RLmin reached -37 dB at 8.64 GHz with the thickness of d=2 mm. With the increase of doping concentration, the minimum reflection loss peak moved to low frequency, and the matching thickness became thicker. The dielectric relaxation polarization, eddy current loss and interference cancellation phenomenon of λ/4 model played the important role in the process of absorption. The double peaks made EG/PANI/Fe3O4 composites possible in the microwave absorption.