Loading...

Table of Content

    10 January 2016, Volume 37 Issue 1
    Content
    Cover and Content of Chemical Journal of Chinese Universities Vol.37 No.1(2016)
    2016, 37(1):  0-0. 
    Asbtract ( )   PDF (2385KB) ( )  
    References | Related Articles | Metrics
    Articles: Inorganic Chemistry
    Preparation of Reduced Graphene Oxide-Copper Sulfide Composite as Efficient Photothermal Agents for Ablation of Cancer
    KONG Xiangquan, YAN Gang, KUANG Miao, RONG Jianhua
    2016, 37(1):  1-7.  doi:10.7503/cjcu20150526
    Asbtract ( )   HTML ( )   PDF (4411KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    A novel reduced graphene oxide-copper sulfide nanoplates(rGO-CuS) composite with photothermal property was synthesized via one-pot hydrothermal method. Structure and morphology of the as-synthesized rGO-CuS nanocomposite were confirmed by transmission electron microscopy(TEM), UV-Vis-NIR and Raman spectroscopy. The rGO-CuS nanocomposite showed enhanced optical absorbance in near infrared region and higher photothermal conversion efficiency than graphene oxide(GO) and CuS nanoplates. The rGO-CuS nanocomposite was further used to photothermal ablation of cancer cells and cancer tissue under a 980 nm laser irradiation and showed improved performance than CuS nanoplates and GO.

    Investigation on the Enrichment of DNA Using Lanthanum Carbonate
    KANG Xiaoyan, HE Anqi, WANG Jingdan, GUO Ran, ZHAI Yanjun, XU Yizhuang, WU Jinguang
    2016, 37(1):  7-11.  doi:10.7503/cjcu20150644
    Asbtract ( )   HTML ( )   PDF (1844KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    The adsorption behavior of Deoxyribonucleic acid(DNA) on lanthanum carbonate particles was investigated. Both UV and XPS results demonstrated that DNA could be adsorbed on the surface of lanthanum carbonate particles. Moreover, the efficiency of adsorption was maximized when the pH value of the solution was set around 5.5. In addition, DNA could be desorpted when lanthanum carbonate particles with adsorpted DNA was dispersed in aqueous solution of KH2PO4. The ICP results demonstrated that the concentration of La3+ was lower than 0.1 μmol/L in the aqueous solution after desorption process, thereby excluding the possibility of undesirable influence on DNA.

    Analytical Chemistry
    Label-free Fluorescence Assay of Telomerase RNA Based on Strand Displacement Amplification
    ZHANG Xiafei, CHENG Rui, SHI Zhilu, JIN Yan
    2016, 37(1):  12-18.  doi:10.7503/cjcu20150524
    Asbtract ( )   HTML ( )   PDF (3097KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    A novel fluorescence method was developed for detecting telomerase RNA(hTR) based on the fluorescence resonance energy transfer(FRET) and strand displacement amplification(SDA) technique. Graphene oxide(GO) served as DNA carrier and fluorescence quencher. SYBR Green Ⅰ(SGⅠ) and hairpin DNAs(hpDNA) are fluorescence probe and molecular recognition probes, respectively. The fluorescence of SGⅠ that intercalated into the stem of hairpin DNAs was quenched when hpDNA1 and hpDNA2 were adsorbed onto the surface of GO. In the presence of T1, the hybridization reaction between hpDNA1 and T1 opened the hairpin structure of hpDNA1 to trigger the SDA reaction between hpDNA2 and T1, leading to an accumulation of hpDNA1/hpDNA2 hybrids. The rigid dsDNA desorbed from GO surface to restore the fluorescence of SGⅠ. Based on the change in fluorescence intensity, T1 can be quantitatively detected from 0.2 nmol/L to 50 nmol/L, with a detection limit of 90 pmol/L. Therefore, it offers a label-free, highly sensitive and specific fluorescence strategy for detection of hTR.

    Chiral Metal-organic Framework{[Co(L-trp)(bpe)(H2O)]·H2O·NO3}n Used for High Performance Liquid Chromatographic Separation
    NONG Ruiyu, KONG Jiao, ZHANG Junhui, CHEN Ling, TANG Bo, XIE Shengming, YUAN Liming
    2016, 37(1):  19-25.  doi:10.7503/cjcu20120521
    Asbtract ( )   HTML ( )   PDF (2842KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    A homochiral MOF {[Co(L-trp)(bpe)(H2O)]·H2O·NO3}n[L-trp=L-tryptophan, bpe=1,2-bis(4-pyridyl)ethylene] with 2D chiral layers was synthesized and used as a new chiral stationary phase for high-performance liquid chromatographic enantioseparation in this study. The chiral MOFs was characterized by powder X-ray diffraction(XRD) and scanning electron microscope(SEM). The experimental results showed that 3 isomers and 11 recemates were separated on {[Co(L-trp)(bpe)(H2O)]·H2O·NO3}n packed column. The chiral column also exhibited good reproducibility and stability.

    Determination of Trace-amount Calcium in Drinking Water by Microwave Plasma Torch Mass Spectrometry
    ZHONG Tao, YANG Meiling, PEI Miaorong, ZHANG Xinglei, LE Zhanggao, WANG Guangcai, CHEN Huanwen
    2016, 37(1):  26-30.  doi:10.7503/cjcu20150503
    Asbtract ( )   HTML ( )   PDF (1128KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    A method for the determination of trace-amount calcium in drinking water by common organic mass spectroscopy was developed. Meanwhile, microwave plasma torch was introduced as ionization source and low-cost ion trap was introduced as mass analyzer. The operation parameters including flow rates of working gas and carrying gas were studied and optimized. Under the optimal experimental conditions, the micro-amount calcium in well water, tap water and bottled water were determined. In order to minimize the matrix effects in the real samples, the standard addition analysis method was employed. The limit of detection was 3.88 ng/L, and the relative standard deviations(RSD) were 2.87%—8.04%. Recoveries were determined between 101.3% and 115.1%. Experimental results indicated that the novel analytical strategy based on MPT-LTQ-MS for qualitation and quantitation of micro-amount calcium in drinking waters was simple and convenient. And its precision and accuracy meet the demand of determination. Furthermore, compared with ICP-MS, MPT-LTQ-MS was low-cost including instrument and maintenance. The proposed method is a novel and promising strategy for detection of micro-amount calcium in drinking waters.

    Disturbance of Troxerutin to Belousov-Zhabotinskii Oscillating System and Its Content Determination
    YE Danni, CAI Zhuo, JIANG Cuiwen, YUE Weichao
    2016, 37(1):  31-36.  doi:10.7503/cjcu20150481
    Asbtract ( )   HTML ( )   PDF (1366KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    A new method for the determination of troxerutin was developed based on the disturbance of troxerutin to Belousov-Zhabotinskii oscillation system. Under optimal conditions, the variation of ΔE had a linear relationship with troxerutin concentration in the range of 0.808—40.4 μmol/L, with detection limit of 2.14×10-7 mol/L(S/N=3). The established method was used to determination of troxerutin in injection, and the recovery was 98.8%—101%. The results showed that the data obtained by this method and the ones by UV method had no significant difference. The possible mechanism was studied using cyclic voltammetry and UV spectrophotometry.

    Preparation and Characterization of L-Tryptophan Molecularly Imprinted Photonic Hydrogels
    YANG Zhaokun, ZHANG Xiaodong, SHI Dongjian, CHEN Mingqing, LIU Shirong
    2016, 37(1):  37-42.  doi:10.7503/cjcu20150434
    Asbtract ( )   HTML ( )   PDF (2953KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Free-standing molecularly imprinted photonic hydrogels(MIPHs) that peeled from the supporters were prepared using the colloidal crystal template method assisted by “sandwich structure”. MIPHs were fabricated by UV polymerization with L-Tryptophan(L-Trp) as template molecule, acrylamide(AM) as functional monomer, N,N'-methylene bisacrylamide(BIS) as crosslinking agent. MIPHs were characterized by highly ordered three-dimensional interconnected macroporous structure. MIPHs showed rapid response property when immersed into L-Trp buffers. The Bragg diffraction peak of MIPHs redshifted 83 nm as the concentration of L-Trp increased from 10-10 mol/L to 10-5 mol/L, and the color changes could be visible by the naked eyes. Moreover, MIPHs showed only a slight shift in the Bragg diffraction peak in solutions of L-Tyr or L-Phe, which indicated that MIPHs possessed a certain selectivity. High selectivety, rapid response and signal self-reporting of MIPHs might provide great convenience for the application in the real-world environments.

    Organic Chemistry
    Solution, Conformational Properties and Morphology of Psyllium Polysaccharide with Ferulic Acid Removal
    YIN Junyi, LIU Xiaoying, NIE Shaoping, XIE Mingyong
    2016, 37(1):  43-47.  doi:10.7503/cjcu20150513
    Asbtract ( )   HTML ( )   PDF (1483KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    This study was aimed at investing the solution and conformation properties of polysaccharide from psyllium(or seeds of Plantago asiatica L.). The fraction which was subjected with NaOH to remove ferulic acid was named as PLCP-FAS, while another fraction was PLCP-FAE whose ferulic acid was removed by feruloyl esterase. Ubbelohde capillary viscometer, HPSEC with refractive index, light scattering and viscometric detectors and scanning electron microscope(SEM) were applied to investigate the two fractions’ solution, conformation properties and solid form. The results showed that there was little change in monosaccharide compositions of the polysaccharide after ferulic acid removing, not mater by NaOH or enzyme. Sugar contents and uronic acid contents were much higher both for the two fractions. However, its apparent viscosity reduced remarkably. Intrinsic viscosity of PLCP-FAS and PLCP-FAE were close either in 0.1 mol/L NaCl or 0.5 mol/L NaOH. HPSEC analysis results showed that weight average molecular weight of PLCP-FAS was 3.17×106, while it was 2.83×106 for PLCP-FAE. Persistence length of PLCP-FAS and PLCP-FAE were similar. SEM results showed that both PLCP-FAE and PLCP-FAS still exhibited certain linear chain characteristics. The above results indicated that the psylliun polysaccharide after removing ferulic acid was semi flexible, and morphology of the polysaccharide remained some linear chain characteristics.

    Synthesis and Structural Analysis of Coil-Rod-Coil Molecules Containing Lateral Groups in the Middle of the Rod Segment
    YANG Yuntian, YU Shengsheng, LI Zhaohua, CHEN Tie, JIN Longyi
    2016, 37(1):  48-53.  doi:10.7503/cjcu20150490
    Asbtract ( )   HTML ( )   PDF (2315KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    A series of triblock coil-rod-coil molecules, containing biphenyl, phenyl and phenyl groups with lateral units linked together with ether as a rod segment and poly(ethylene oxide)(PEO) which have a polymerization degree of 7, 12, 17, as the coil segment, was synthesized. Molecular structures of these compounds were characterized by means of 1H NMR and MALDI-TOF MS. The self-assembling behavior of the molecules was investigated by means of differential scanning calorimetry(DSC), small-angle X-ray scattering(SAXS) and optical polarized micrograph(POM) in the bulk state. The molecules 1a—1c spontaneously self-assembled into lamellar, hexagonal perforated lamellar, oblique columnar structure, while molecules 2a—2c self-assembled into oblique columnar and body-centered tetragonal structures in the crystalline phase, respectively. The results revealed that the lateral groups attached to the middle of rod segments dramatically influence the self-assembling behavior of these rod-coil molecular system.

    Microwave Synthesis of Glycerol Carbon Quantum Dots and Its Application in Fe3+ Probe
    ZHANG Jing, JIANG Yuliang, CHENG Yu, GU Weijin, WANG Bingxiang
    2016, 37(1):  54-58.  doi:10.7503/cjcu20150436
    Asbtract ( )   HTML ( )   PDF (2451KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Glycerol was selected as sole starting material by one step microwave method for prepared a new type of carbon quantum dots(CDs). The size of th CDs distribute in 4—25 nm with the average particle size of 16.5 nm. In addition, the resulting CDs could exhibit a highly sensitive fluorescence response behavior to Fe3+ compared to other 13 kinds of metal ions including Cu2+, Ca2+, Zn2+, Co2+, Fe2+, Ni2+, Mn2+, Na+, Cd2+, Mg2+, Pb2+, K+ and Ag+. The detection limit of Fe3+ was calculated to be 2 μmol/L with a linear dynamic range of 10—60 μmol/L.

    Alternating Copolymerization of Aryl Aldehyde Imines and Carbon Monoxide
    LÜ Haoting, MIAO Qun, SUN Huailin
    2016, 37(1):  59-64.  doi:10.7503/cjcu20150421
    Asbtract ( )   HTML ( )   PDF (1409KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Alternating copolymerization of aryl aldehyde imines and CO, using phenylacetyl tetracarbonyl cobalt as catalyst, was investigated in details. The reactions were carried in dioxane at 50 ℃ under 6 MPa of CO pressure, and six new polypeptide products were obtained from copolymerization of the corresponding aryl imines and CO. The steric and electronic effects of substituents at the phenyl rings were examined, which showed obvious influences on the molecular weight of the polymerization products as well as the copolymerization. The structures of the polypeptide products were characterized by naclear magnetic resonance(NMR), Infrared(IR), gel permeation chromatography(GPC) as well as matrix-assisted laser desorption/ionization time of flight mass spectrometry(MALDI-TOF MS) methods. According to the MS results, there existed three kinds of new end group structures at the terminal ends of the polymerization products, which should correspond to münchnone, imidazoline and amide structures, respectively. Possible mechanisms for the formation of the three kinds of end groups were discussed.

    Physical Chemistry
    Study on the Adsorption Ability to Linear Alkylbenzene Sulfonate of Zeolite P Modified by Cetrimonium Bromide in Waste Water
    TAN Wenyuan, XU Man, ZENG Ying
    2016, 37(1):  65-72.  doi:10.7503/cjcu20150667
    Asbtract ( )   HTML ( )   PDF (3063KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Zeolite P(PZ) was prepared by the natural clinoptilolite(Z) that was treated with lye, and then Z and PZ were modified by cationic surfactant cetrimonium bromide(CTMAB) to prepare ZC and PZC. The adsorption abilities of ZC and PZC to linear alkylbenzene sulfonate(LAS) were studied. The results indicated that the Si/Al ratio of PZ was 2, 58.8% lower than that of Z(4.85); the point of zero net charge(PZNC), specific surface area, pore radius and pore volume of PZ were higher than those of Z; the adsorption equilibrium was reached after 4 h. ZC and PZC had a maximum adsorption capacity for LAS at pH=2. The adsorption process was well fitted with pseudo-second order kinetic equation and Langmuir isothermal adsorption model. The amount of saturated adsorption of ZC and PZC are 12.658 and 27.100 mg/g, respectivey, showing that the adsorption process is described primarily for the monolayer and chemical adsorption, the adsorption of LAS on PZC is better than that on ZC in view of point of capacities and velocities.

    Preparation and Electrochemical Energy Storage Performances of Carbon Nanotube Network/Polyaniline Composite
    JIANG Qi, CHEN Jiankang, CHEN Zi, HE Lamei, LU Xiaoying, HU Ailin
    2016, 37(1):  73-78.  doi:10.7503/cjcu20150579
    Asbtract ( )   HTML ( )   PDF (1977KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Using the carbon nanotube(CNT) powder and carbon nanotube network(CNTN) as the template, CNT/polyaniline(PANI) and CNTN/PANI composites were prepared via a PANI finite field polymerization method. The morphologies of the obtained samples were characterized by transmission electron microscope and scanning electron microscope. Nitrogen adsorption-desorption analysis was used to study the composites’ pore structure data, and the four-probe conductivity meter was also used to study the samples’ electric conductivity. The electrochemical energy storage performance of the obtained materials was characterized the cyclic voltammograms, galvanostatic charging/discharging curves, cycle life testing and electrochemical impedance spectroscopy. The results show that the obtained CNTN/PANI composite has higher electrochemical capacitance of 143.2 F/g(in organic electrolyte) and better electrical conductivity than the CNT/PANI, indicating that CNTN is more suitable to prepare composite with polymer than CNT powder since the CNTN has outstanding electrical conductivity, mechanical property and electrochemical energy storage property.

    Mechanism and Kinetics of the Hydrogen-abstraction Reaction of CF2ClC(O)OCH2CH3 with OH Radicals
    ZHU Peng, DUAN Xuemei, LIU Jingyao
    2016, 37(1):  79-87.  doi:10.7503/cjcu20150568
    Asbtract ( )   HTML ( )   PDF (4499KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    The mechanism of the hydrogen abstraction reaction of CF2Cl(O)OCH2CH3+OH was studied theoretically via a dual-level direct dynamics method at the MCG3-MPWB//M06-2X/aug-cc-pVDZ level. Five stable conformers(RC1—RC5) of the reactant CF2Cl(O)OCH2CH3 were located, and for each conformer, the possible H-abstraction channels from —CH3 and —CH2— groups were taken into account. The rate constants were calculated using the improved canonical variational transition-state theory(ICVT) with the small-curvature tunneling correction(SCT) and the selectivity of the reaction sites of CF2Cl(O)OCH2CH3 was evaluated. The results show that for the conformers RC1 and RC2, the H-abstraction reactions mainly take place at the —CH2— group at low temperature, while for the conformers RC3, RC4 and RC5, the hydrogen abstraction from the —CH3 group is the major channel in the whole considered temperature range. The overall rate constant is obtained by considering the weight factors of the five conformers calculated from the Boltzmannn distribution function. It is found, that the calculated koverall at 298 K is in good agreement with the available experimental data. The three parameter expression for the overall reaction within 200—1000 K is fitted to koverall=5.45×10-25 T4.54 exp(-685/T).

    Synthesis, Photocatalytic Activity and Regeneration of AgBr/CuO Heterojunction Photocatalyst
    ZHANG Xue, LIU Jianxin, WANG Yawen, FAN Caimei, DUAN Donghong, WANG Yunfang
    2016, 37(1):  88-93.  doi:10.7503/cjcu20150522
    Asbtract ( )   HTML ( )   PDF (2462KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    AgBr/CuO p-n heterojunction photocatalyst was prepared by precipitation method and characterized by X-ray diffraction(XRD), UV-Vis spectroscopy(UV-Vis), field emission scanning electron microscopy(FESEM) and X-ray photoelectron spectroscopy(XPS), respectively. The photocatalytic mechanism was speculated through active species test and band structure analysis. Besides, the used AgBr/CuO was regenerated by 3%(mass fraction) bromine water. The results show that the degradation rate of methyl orange(c0=15 mg/L) over 0.1 g AgBr/CuO was maintained at 92% after 30 min, which was much higher than that over pure AgBr under the same conditions. The reasons for improving the photocatalytic activity of AgBr/CuO photocatalyst are that the band gap of AgBr/CuO photocatalyst become wider and the p-n heterojunction structure is formed between AgBr and CuO. The wider band gap was benefit for the redox ability of photogenerated electrons and photogenerated holes. The p-n heterojunction structure of photocatalyst could accelerate the shift of electrons and the separation of e--h+. In addition, the use of bromine water regeneration method could significantly restore photocatalytic activity.

    Catalytic Mechanism of Ionic Liquid for CO2 Electrochemical Reduction
    YANG Dongwei, LI Lu, WANG Qin, WANG Xiaochun, LI Qingyuan, SHI Jin
    2016, 37(1):  94-99.  doi:10.7503/cjcu20150514
    Asbtract ( )   HTML ( )   PDF (1501KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    In 1-butyl-3-methylimidazolium trifluoromethanesulfonate([Bmim][CF3SO3])/propylene carbo-nate(PC) solution, the rate-determining step and catalytic mechanism of ionic liquid for CO2 electrochemical reduction on gold electrode were studied by cyclic voltammetry, electrochemical impedance spectroscopy and impedance simulation. Experimental results show that the rate-determining step for CO2 reduction is the formation of C radical by one-electron transfer. Due to the catalytic effect of ionic liquid, the onset potential of CO2 reduction in [Bmim][CF3SO3]/PC shifts positively by 239 mV comparing to that occurred in tetrabuty-lammonium trifluoromethanesulfonate([Bu4N][CF3SO3])/PC catholyte. The catalytic mechanism of ionic liquid is proposed as follows: firstly, the cation of ionic liquid([Bmim]+) adsorbed on the Au electrode and lead to the formation of ionic liquid film; then, CO2 in catholyte diffuses from the bulk solution to the surface of cathode. After transfer through the ionic liquid film adsorbed on the surface of Au electrode, CO2 is reduced to C radical via single electron transfer. The generated C radical further react with cation [Bmim]+ and induce the formation of [Bmim-CO2]ad. Through this route, the activation energy of CO2 electrochemical reduction is reduced. Hence the overpotential of CO2 electrochemical reduction is reduced substantially.

    Effects of External Electric Field on Hydrogen Storage Performance of Li-decorated Graphene Oxide
    ZHAO Han, ZHOU Lina, WEI Dongshan, ZHOU Xinjian, SHI Haofei
    2016, 37(1):  100-107.  doi:10.7503/cjcu20150472
    Asbtract ( )   HTML ( )   PDF (3053KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Hydrogen storage performance of Li decorated graphene oxide(GO) under an external electric field was investigated with the first-principle method based on the density functional theory(DFT) calculations. Firstly the stability of Li@GO structure due to the adsorption of Li atoms at different binding sites on GO structure was investigated. Then a stable Li@GO structure was obtained and dependences of the structural stability and H2 adsorption of the Li@GO structure on the electric field were discussed. The results indicate that both the H2 adsorption energy, Ead, and the distance between H2 and Li atom, d(Li-H2), decrease with the increasing intensity of the downward electric field. While both Ead and d(Li-H2) increase with the increasing intensity of the upward electric field. From the partial density of state(PDOS) analysis, the H2-Li hybridization peaks under a negative electric field shifted to the larger negative energy region compared to those without an electric field, which indicates the H2-Li@GO system becomes more stable under the negative electric field. When the positive electric field was added, the H2-Li hybridization peaks shifted to the smaller negative energy region, which indicates the interaction between H2 and Li becomes weaker. It is therefore anticipated that the adsorption-desorption processes of H2 on Li@GO structure can be easily controlled by adding an electric field with appropriate intensity and direction. Further calculation indicates the Li@GO structure has a maximum hydrogen storage capability of larger than 3.1% without the external electric field.

    Paal-Knorr Reaction Catalyzed by Fe-MIL-101 for Efficient Synthesis of Pyrroles
    YANG Ming, TANG Jia, WANG Jingjing, FAN Shuang, ZHANG Huan, TAO Liushi, TAN Li
    2016, 37(1):  108-113.  doi:10.7503/cjcu20150462
    Asbtract ( )   HTML ( )   PDF (2318KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    A highly porous metal-organic frameworks(Fe-MIL-101) was synthesized as a heterogeneous catalyst for the Paal-Knorr reaction. The free coordination position of Fe(Ⅲ) in Fe-MIL-101 can be used as catalytic active sites for the Paal-Knorr reaction. The large surface area and pore size of Fe-MIL-101 contribute to offer an access for organic substrates to the active sites sufficiently, which ensure a high catalytic performance of Fe-MIL-101 for pyrroles. The catalyst could be reused five times without loss of its catalytic activity. In addition, the catalyst also exhibits high catalytic activity in other amines system with 2,5-hexane-dione for Paal-Knorr condensation reaction.

    Effect of Metal Particle Size on the Performance of Tethered-phosphine Modified Rh/SiO2 in Hydroformylation
    LIU Jia, YAN Li, JIANG Miao, DING Yunjie
    2016, 37(1):  114-120.  doi:10.7503/cjcu20150450
    Asbtract ( )   HTML ( )   PDF (3169KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    A series of tethered-phosphine modified Rh/SiO2 catalysts with different Rh particle size was prepared by preparation technology of shell-type catalyst, which shared the same Rh loading and P/Rh ratio. Ethylene hydroformylation was used as a probe reaction to test the performance of those catalysts. The results show that Rh particle size has a great effect on the performances of phosphine modified Rh/SiO2 catalysts. The catalytic activity increased as Rh particle size decreased, but meanwhile the induction period prolonged. The catalysts were characterized by H2 chemical adsorption, transmission electron microscope, N2 adsorption-desorption isotherms, in situ Fourier-transform spectra and solid 31P nuclear magnetic resonance technology. The active species were Rh-phosphine complex, and more amount of active species were produced over catalyst with smaller Rh particle size. With the decreasing of Rh particle size, the density of Rh particle on the surface decreased and it took more time for DPPPTS to reach Rh and form Rh-phosphine complex.

    Theoretical Studies on the of Ambipolar Charge Transport in Terazulene Single Crystal
    CHEN Jiuju
    2016, 37(1):  121-125.  doi:10.7503/cjcu20150446
    Asbtract ( )   HTML ( )   PDF (1611KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    The quantum chemical calculations and the Marcus charge transfer theory were combined to study the charge transport property for holes and electrons in the terazulene single crystal. The angular resolution anisotropic and average charge mobilities were obtained simultaneously from a set of identical trajectories with random walk technique. Meanwhile, Terazulene showed similar molecular conjugation to naphthodithiophene, which was a good hole transport material. The different types of charge transport for terazulene and naphthodithiophene were analyzed, which provided insight for the influence of the molecular structures on the charge transport from a theoretical viewpoint.

    Mesoporous TiO2 as the Anode Catalyst Support for Solid Polymer Electrolyte Water Electrolysis
    CHEN Gang, MI Cangen, LÜ Hong, HAO Chuanpu, HUANG Yu, SONG Yukun
    2016, 37(1):  126-133.  doi:10.7503/cjcu20150442
    Asbtract ( )   HTML ( )   PDF (6234KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    TiO2 support was prepared through evaporation-induced self-assembly(EISA) by using butyl titanate as starting material. Three TiO2 samples were calcined at different temperatures and then IrO2 was loaded on them with a mass ratio of IrO2/TiO2 of 2/3 by a modified Adams fusion method. The samples were characterized by X-ray diffraction(XRD), specific surface area measurement, thermogravimetric and differential scanning calorimetry analysis(TGA-DSC), transmission electron microscopy(TEM) and electrochemical testing. The electrochemical activity of the catalysts was investigated in a single cell proton exchange membrane(PEM) electrolyzer consisting of a Pt/C cathode and a Nafion117 membrane. The results suggested that as the calcination temperature increased, the mesoporous structure of TiO2 was destroyed, the pore size increased and the pore volume reduced, and the phase of TiO2 transferred from anatase to rutile structure. Utilization of the TiO2 support resulted in a reduction in the size of the IrO2 crystallites and improved the distribution of catalyst. It was found that the lower the specific surface area of the support was, the higher the electrochemical activity of the catalyst was. This is most likely due to the formation of a conductive IrO2 film on the surface of non-conductive supports with 40%(mass fraction) loading of IrO2. The IrO2, 40%IrO2/TiO2-2 and 40%IrO2/TiO2-3 catalysts showed a polarization potential of 2.024, 2.426 and 2.064 V, respectively, under a current density of 1.0 A/cm2. These results suggest that the surface structure of the support has a great influence on the catalytic activity of IrO2.

    Effect of Fuel on Structure and Catalytic Performance for Slurry Methanation over Ni-Al2O3 Catalysts Prepared by Combustion Method
    JI Keming, MENG Fanhui, GAO Yuan, LI Zhong
    2016, 37(1):  134-141.  doi:10.7503/cjcu20150389
    Asbtract ( )   HTML ( )   PDF (7146KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    A series of Ni-Al2O3 catalysts was prepared by impregnation combustion method and co-combustion method, and the catalysts were characterized by N2 adsorption-desorption, XRD, TEM, H2-TPR and H2 chemisorption. The effect of fuel type on structure and catalytic methanation performance over Ni-Al2O3 catalysts in a slurry-bed reactor was studied. The results show that Ni-Al2O3 catalysts, prepared by impregnation combustion method using urea, glycine or ethylene glycol as fuel, exhibited similar textural properties, metallic Ni dispersion and Ni crystallite size as those of the support, and the CO conversion was between 80.1% and 83.5% at 260 ℃. However, the Ni-Al2O3 catalysts, prepared by co-combustion method, were significantly affected by the combustion process. The specific surface area of the catalysts prepared using glycine and ethylene glycol as fuel was small, and the metallic Ni dispersion was low and Ni crystallite size was large, which resulted in the low CO conversion. The Ni-Al2O3 catalyst using urea as fuel exhibited the large specific surface area and metallic Ni dispersion and small Ni crystallite size, and the CO conversion and CH4 selectivity reached 84.7% and 91.1%, respectively.

    Electrochemical Impedance Spectroscopy of Dichlorophenols at Boron-doped Diamond Electrodes
    LÜ Jiangwei, QU Youpeng, FENG Yujie, LIU Junfeng
    2016, 37(1):  142-148.  doi:10.7503/cjcu20150369
    Asbtract ( )   HTML ( )   PDF (3053KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Cyclic voltammetry(CV) and electrochemical impedance spectroscopy(EIS) were used to investigate the electrocatalytic process of boron-doped diamond(BDD) electrode with 2,4-dichlorophenol(2,4-DCP) and 2,6-dichlorophenol(2,6-DCP) as target pollutants. Results showed that the oxidation potential of the 2,4-DCP and 2,6-DCP were 1.55 and 1.62 V, respectively. Equivalent circuit simulation results showed that the charge transfer resistance for the two DCPs were both decreased when the polarization potential increased from open circuit potential to 1.5 V, indicating that electrocatalytic oxidation was favored by increasing potential. The diffusion step was the control step at oxidation potential. The indirect electrochemical oxidation of 2,4-DCP occurred more easily at BDD electrode than 2,6-DCP.

    Polymer Chemistry
    Synthesis, Electrochromic and Non-volatile Memory Performance of Poly(triarylamine) Containing Functional Quaternary Ammonium Salt
    LIANG Yu, WANG Benfu, ZHANG Qian, BAI Xuduo, WANG Yanqiu, REN Decai, NIU Haijun
    2016, 37(1):  149-154.  doi:10.7503/cjcu20150696
    Asbtract ( )   HTML ( )   PDF (2433KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Two novel poly(triphenylamine) containing functional quaternary ammonium salt(PTP3FQ and PP3FQ) were prepared from two dibromo aromatic compounds, bis(4-bromophenyl) ether and p-dibromobenzene, and 4-(4-aminophenoxy)pyridine via Buchwald-Hartwig coupling reaction, followed by quaterisation reaction with 3-chloromethyl-5-[3-(trifluoromethyl) phenyl]-1,2,4-oxadiazole. The resulting polymers were characterized by 1H nuclear magnetic resonance(1H NMR), Fourier transform infrared(FTIR), thermogravimetry analysis(TGA) and cyclic voltammogram. PTP3FQ and PP3FQ not only showed good electrochromic properties withoutadding any electrolyte but also exhibited non-volatile memory performance with a large ON/OFF ratio over 103 due to the charge transfer between donor triphenylamine and acceptor oxadiazole.

    Synthesis and Proporties of Temperature and pH-sensitive and Gadolinium Contained Polymeric Magnetic Resonance Imaging Contrast Agent
    LIU Ruiqing, LIANG Shuang, JIANG Cun, XU Zushun, XU Haibo
    2016, 37(1):  155-160.  doi:10.7503/cjcu20150663
    Asbtract ( )   HTML ( )   PDF (2838KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Paramagnetic, temperature and pH-sensitive polymeric particles were prepared with N-isopropylacrylamide, methacrylic acid, styrene, and polymerizable Gd(AA)3phen·H2O using emulsifier-free emulsion polymerization technique. Dynamic light scattering result shows that the diameter of the polymeric particles changes by about 60 nm as a result of variations in either the temperature or pH, indicating that the particles are pH and temperature-sensitive. The T1-weighted relaxivity values at 3 T are about 11.3 L/(mmol·s) which is 2.6 times higher than clinical Magnevist?. In vivo MR imaging reveals that the TPRPPs can be effectively imaged in the liver and spleen, suggesting that they are excellent magnetic resonance imaging agents.

    Novel Method of Preparation of Diblock Copolymers with Disulfide Bonds at Junction Points
    ZHANG Lixin, WANG Jintao, YANG Yongfang, ZHAO Hanying
    2016, 37(1):  161-166.  doi:10.7503/cjcu20150570
    Asbtract ( )   HTML ( )   PDF (2944KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Synthesis of diblock copolymers containing disulfides at the junction points was reported. Rever-sible addition-fragmentation chain transfer(RAFT) polymerization of styrene was employed to prepare polystyrene marco RAFT agent(PS-RAFT). The terminal RAFT agents of PS were reduced to sulfhydryl groups(PS-SH) in the presence of primary amine, and the atom transfer radical polymerization(ATRP) macroinitiator(PS-S-S-ATRP) was prepared by an exchange reaction between PS-SH and an ATRP initiator containing disulfide bonds. PS-S-S-ATRP was used to initiate the polymerization of 2-hydroxyethyl methacrylate(HEMA) and PS-S-S-PHEMA diblock copolymers with disulfides at the junction points were obtained. The structures and molecular weights of the diblock copolymers were characterized by proton nuclear magnetic resonance(1H NMR) and gel permeation chromatography(GPC). Kinetics study of ATRP of HEMA shows the characteristic of living polymerization. In methanol, the diblock copolymer self-assembles into polymeric micelle with PS cores and PHEMA coronae. Transmission electron microscopy and dynamic light scattering were used to study the morphology changes of the micelles after cleavage of the disulfide bonds. The result shows a new methd to prepare block copolymers with disulfide bonds at the junction points. The self-assenbly strecture of the copolymers will have a wide application in drug release and biological imaging techniques.

    Composition and Molecular Weight Determination of Aqueous Two-phase System by Quantitative Size Exclusion Chromatography
    ZHAO Ziliang, LI Qi, XUE Yanhu, JI Xiangling, BO Shuqin, LIU Yonggang
    2016, 37(1):  167-173.  doi:10.7503/cjcu20150567
    Asbtract ( )   HTML ( )   PDF (1292KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Quantitative size exclusion chromatography(SEC) was exploited to study the composition, molecular weight and molecular weight distribution of aqueous two-phase system of dextran and poly(ethylene glycol)(PEG) following phase separation. Tie lines constructed by SEC method were compared with the cloud point curve of the system obtained by titration. An excellent agreement was found between the tie line end points and the cloud point, except for the data points of the PEG-rich phases close to the critical point. The molecular weight and molecular weight distribution of the two polymer species in two co-existing phases obtained by SEC indicate that the mismatch is caused by the uneven distribution of macromolecular components between two phases upon phase separation. Having a broad molecular weight distribution, dextran in the two phases show prominent molecular mass difference. The molecular weight of dextran in the dextran-rich phase is significantly higher than that in the PEG-rich phase. As the initial polymer concentration of the system increases, the molecular weight difference of dextran in the two phases becomes more significant. However, we have not observed such a trend for PEG because of its narrow molecular weight distribution. Accurate data on the phase diagram and molecular weight of two polymer components in the co-existing phases can be obtained using quantitative SEC. The above results will not only help to understand the phase diagram of dextran-PEG-water ternary system, but also provide guidance to its application in extraction and separation of biological materials.

    Morphology Evolution of Thin Polystyrene Film During the Non-solvent Driven Dewetting Process
    XU Lin, ZHANG Huanhuan, SHI Tongfei
    2016, 37(1):  174-179.  doi:10.7503/cjcu20150553
    Asbtract ( )   HTML ( )   PDF (5254KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    We investigated the dewetting process of thin polystyrene(PS) film induced by different non-solvents via atomic force microscope(AFM). It is found that the non-solvent induced dewetting of thin PS film is via the penetration-replacement mechanism. The morphology of thin PS film depends on the relative velocity of the hole forming process and the hole growth process. When the thickness of PS film is 15 nm, with the increase of the alkyl chain of solvents, the number of holes significantly decreased, while the size of the holes obviously increased. When the thickness of PS film increased to 25 nm, with the increase of the alkyl chain of solvents, the formation of the number of holes is slightly low and the film morphology is a long-range ordered double continuous structure. When the PS film thickness is 35 nm, the number of holes decreased significantly comparing with the other two films. In addition, temperature and molecular weight can further reduce the number of holes in the process of dewetting and form fractal morphology.

    Preparation, Characterization and Application of Silica Nanoparticle Micro-aggregates with Circular Structure
    TIAN Min, YANG Yingjuan, HE Wentao, LI Juan, QIN Shuhao, YU Jie
    2016, 37(1):  180-188.  doi:10.7503/cjcu20150510
    Asbtract ( )   HTML ( )   PDF (11491KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Silica sol was firstly prepared by means of sol-gel method and then dried by spray drying method. Scanning electronic microscope(SEM) results demonstrated that the initially obtained nanoparticles were recomposed to monodispersed circular aggregates with size about 20 μm. The silica/polypropylene(PP) composite was prepared and investigated by means of differential scanning calorimetry(DSC), polarizing microscopy(POM), wide angle X-ray diffraction(WAXRD) and transmission electron microscopy(TEM). The micron circular aggregates, PC16MS, broke up and re-dispersed into nanoparticles with size less than 200 nm in the PP matrix during melt-compounding. The effect of the addition of PC16MS on spherulite growth of iPP was investigated using POM. The results demonstrated that the addition of PC16MS can significantly accelerate the primary nucleation process, minimize the spherulite radius and shorten the crystallization time. A linear relationship was observed between the radius of spherulites and crystallization time at the initial stage of crystallization. With the addition of 2%(mass fraction) PC16MS, the crystallization temperature increased by 10.4 ℃ and the nucleation efficiency reached 39.1% compared to pristine iPP, suggesting PC16MS can be used as an effective nucleating agent for PP.

    Preparation of AOPAN/PA-66 Composite Nanofibers and Its Adsorption of Metal Ion
    YAN Chunqiu, LIU Bin, LU Guanxiu, LI Yaoxian, YANG Qingbiao, SONG Yan
    2016, 37(1):  189-194.  doi:10.7503/cjcu20150459
    Asbtract ( )   HTML ( )   PDF (3670KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    A kind of polyacrylonitrile(PAN) nanofibers which was reinforced with nylon(PA-66) fiber was fabricated via twin-spinneret electrospinning technology, then together with hydroxylamine hydrochloride produce oximation reaction to prepare the amidoxime modified polyacrylonitrile/nylon composite nanofibers(AOPAN/PA-66). The composition, morphology and mechanical properties of the nanofibers before and after oximation reaction were characterized by Fourier transform infrared spectroscopy and scanning electron microscope, and the adsorption properties were evaluated with Cu(Ⅱ) and Pb(Ⅱ). The results show that the compound fiber membrane have great mechanical properties with the tensile strength of 4.73 MPa, elongation at break is 30.76% and when the concentration of heavy metal ion is 500 mg/L, the highest adsorption capacity of AOPAN/PA-66 nanofiber membrane for Cu(Ⅱ) and Pb(Ⅱ) are 67.5 and 75.4 mg/g respectively.

    Preparation and Biological Evaluation of Electrospun Nano-silver/Anisodamine/PLGA
    CUI Weiwei, GAO Tianlin, LU Ying, ZHANG Peibiao, LIU Ya, LI Bo
    2016, 37(1):  195-200.  doi:10.7503/cjcu20150475
    Asbtract ( )   HTML ( )   PDF (3947KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Nano-silver powders(n-Ag)/Anisodamine(AD)/poly(lactide-co-glycolide)(PLGA) were prepared by electrospinning. Field emission scanning electron microscope(ESEM) and Fourier transform infrared spectroscopy(FTIR) were applied for the investigation of the microscopic structure of the dressings as well as drug release, antibacterial and biological functions so that we could comprehensively evaluate the functionality of the dressings. The results show that the fibers exhibit a fully interconnected pore structure with narrow pore size distribution. And the diameters of electrospun fibers are influenced by the incorporation of AD. The result of drug release test proves that anisodamine can gradually release. It is also found that the n-Ag/AD/PLGA dressings exhibit a well antibacterial ability. The cell experimental results show that when the content of AD is from 1% to 5%, the dressings are non-toxic and contribute to the growth and proliferation of mouse L929 cells. Therefore, we conclude that the n-Ag/AD/PLGA dressing possesses good biocompatibility, antibacterial properties, and effectively release. It provides a new strategy for clinical treatment in diabetic foot infection.