Loading...

Table of Content

    10 October 2015, Volume 36 Issue 10
    Articles: Inorganic Chemistry
    Synthesis and Photoelectrical Properties of Self-host Blue-green Phosphorescent Iridium(Ⅲ) Complexes
    SUN Jing, DONG Hailiang, WANG Hua, MIAO Yanqin, XU Huixia, LI Jie, WU Yuling, XU Bingshe
    2015, 36(10):  1859-1864.  doi:10.7503/cjcu20150440
    Asbtract ( )   HTML ( )   PDF (1546KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    A kind of self-host blue-green phosphorescent Ir(Ⅲ) complexes [(CzPhBI)2Ir(tfmptz), (CzPhBI)2Ir(tfmpptz) and (CzPhBI)2Ir(fpptz)] was designed and synthesized. CzPhBI, tfmptz, tfmpptz and fpptz were 9-[6-(2-phenyl-1-benzimidazolyl)hexyl]-9-carbazole, 2-(5-trifluoromethyl-1,2,4-triazolyl)pyridine, 2-[5-(4-trifluoromethyl)phenyl-1,2,4-triazolyl]pyridine and 2-[5-(4-fluoro)phenyl-1,2,4-triazolyl]pyridine, respectively. The structures were confirmed by nuclear magnetic resonance(1H NMR and 19F NMR) and elemental analysis. Photophysical properties were investigated. Electroluminescent performance of Ir(Ⅲ) complexes were characterized by fabricating the non-doped devices with the configuration of indium tin oxid(ITO)│N,N'-bis-(1-naphthalenyl)-N,N'-bis-phenyl-(1,1'-biphenyl)-4,4'-diamine(NPB)(30 nm)│4,4'-Bis(9-carbazolyl)-1,1'-biphenyl(CBP)(15 nm)│Ir complexes(30 nm)│1,3,5-tris(1-phenyl-1H-benzo[d]imidazol-2-yl)benzene(TBPI)(30 nm)│LiF(1 nm)│Al(100 nm). The maximum luminance of (CzPhBI)2Ir(tfmpptz) complexes was 6913 cd/m2 and the maximum luminous efficiency achieved 13.9 cd/A.

    Synthesis of Broad Color-emitting CuInS2/ZnS Quantum Dots at Low Temperature
    FU Min, LUAN Weiling, TU Shantung, MLECZKO Leslaw
    2015, 36(10):  1865-1872.  doi:10.7503/cjcu20150415
    Asbtract ( )   HTML ( )   PDF (2879KB) ( )  
    References | Related Articles | Metrics

    CuInS2/ZnS(CIS/ZnS) quantum dots(QDs) were synthesized below 200 ℃ with zinc diethyl dithiocarbamate(ZDC) as ZnS precursor materials and trioctylphosphine(TOP) as the main capping ligands. The influence of ZDC amount, shell growth temperature and ligands on the optical properties and quantum yield of CIS/ZnS quantum dots were investigated. The results showed that the growth of ZnS shell could happen above 150 ℃ and ZnS growth speed was accelerated by increasing temperature. The absorption peak of prepared CIS/ZnS using TOP as ligands was defined as exctionic absorption through photoluminescence(PL) spectromety and X-ray diffraction analysis. The samples were characterized by PL spectrometer, high resolution transmission electron microscope, energy dispersive X-ray spectrometer and Fourier transform infrared spectrometer. The results showed that ligands of TOP and dodecanethiol were overcoated on the surface of nanoparticles as organic layer, which would affect optical properties and crystal growth speed. TOP could increase the shell growth speed and the CIS/ZnS QDs with uniform size were obtained. The PL emission wavelength could be extended to 550 nm.

    In situ Biomimetic Mineralization and Characterization of Carbon Nanotubes/chitosan Composite Microspheres
    NIU Lulu, HUANG Di, DU Jingjing, WEI Yan, HU Chaofan, YE Jiaye, CHEN Weiyi
    2015, 36(10):  1873-1879.  doi:10.7503/cjcu20150346
    Asbtract ( )   HTML ( )   PDF (6207KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Carbon nanotubes/chitosan(CNTs/CS) composite microspheres were prepared by emulsification and cross-linking method. Nano-hydroxyapatite crystals were biomimetically formed on the surface of the composite microspheres. The influence of CNTs on the mineralization of the microspheres was investigated. The morphologies, structurs and stability properties of the microspheres before and after mineralization were studied through scanning electronic microscopy(SEM), X-ray diffraction(XRD), swelling ratio and water content tests. The results show that the formation ability of the nano-hydroxyapatite on the CNTs/CS microspheres is significantly higher than that on pure CS microspheres. And the mineralized CNTs/CS microspheres exhibit better structure stability. After culturing with MG63 cells for 7 d, the proliferation of cells cultured with mineralized CNTs/CS microspheres shows significant difference from that of the cells cultured with mineralized CS microspheres.

    Analytical Chemistry
    Preparation of Label-free C-Reactive Protein Immunosensor Based on the Palladium-coordinated Covalent Organic Frameworks(Pd/COF-LZU1) Material
    LIU Tingzhi, XIA Jieren, LI Yao, CHEN Wenkai, ZHANG Shuai, LIU Yi, ZHENG Li, YANG Yunhui
    2015, 36(10):  1880-1887.  doi:10.7503/cjcu20150344
    Asbtract ( )   HTML ( )   PDF (3813KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    A new imine-linked covalent organic framework(COF) material was synthesized using organic monomer via solvothermal methods. Pd(Ⅱ)-coordinated COF, Pd/COF-LZU1, was accordingly synthesized through simple post-treatment at ambient conditions, which showed excellent catalytic activity. Then, a label-free C-reactive protein(CRP) immunosensor was constructed using the Pd/COF-LZUI porous composite material to immobilize anti-CRP on the surface of GCE. When anti-CRP binds with CRP antigen, the formed immuno complex obstruct the electric signal of Fe(CN)64-/3-, which can be used to realize label-free detection of CRP. Electrochemical impedence spectroscopy(EIS) and differential pulse voltammetry(DPV) were employed to characterize the immunosensor. The experimental conditions such as scanning rate, pH value of testing solution, the concentration of anti-CRP and incubation time were also optimized. Under the optimal experimental conditions, the linear range was 5—180 ng/mL, the detection limit was 1.66 ng/mL, with the linear correlation coefficient of 0.992. This immunosensor provides a novel and simple way to detect CRP, and develops the application of the COFs in the electrochemical immunosensor.

    Electrochemical Sensing of 1-Naphthylamine Based on Multiwalled Carbon Nanotubes@graphene Oxide Nanoribbons Core-shell Heterostructure
    ZHU Gangbing, PEI Yuanpeng, CHEN Yuxuan, YI Yinhui, SUN Heng, WU Xiangyang
    2015, 36(10):  1888-1893.  doi:10.7503/cjcu20150343
    Asbtract ( )   HTML ( )   PDF (3996KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    A novel core-shell heterostructure with multiwalled carbon nanotubes(MWCNTs) as the core and graphene oxide nanoribbons as the shell(MWCNTs@GONRs) was prepared from longitudinal partially unzipping of MWCNTs and applied in electrochemical sensing of 1-naphthylamine(1-NA). Scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy and thermogravimetric analysis were used to characterize the morphology and structures of MWCNTs@GONRs. Owing to the synergistic effects from MWCNTs and GONRs, the oxidation peak current of 1-NA at the MWCNTs@GONRs modified glassy carbon electrode(GCE) are much higher than those at the MWCNTs/GCE and bare GCE, and the MWCNTs@GONRs/GCE has a linear response range of 8.0—400.0 nmol/L with a detection limit of 2.5 nmol/L for 1-NA determination.

    Metabolism of Ginsengside Rb1 in Rat Liver Microsomal in vitro by HPLC-MS and Cocktail Probe Substrats Method
    WANG Yibo, XIAO Dan, LI Xiaoyu, DAI Yulin, YUE Hao, LIU Shuying
    2015, 36(10):  1894-1899.  doi:10.7503/cjcu20150307
    Asbtract ( )   HTML ( )   PDF (2165KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    The effect and metabolisms of ginsenoside Rb1 were studied on cytochrome P450s(CYP450). The induction or inhibition effects of CYP450 enzymes were evaluated by investigating the changes of probe drug in concentration. The metabolites of ginsenoside Rb1 including ginsenoside Rd, ginsenoside F2 and the oxidation of ginsenoside Rb, were found and identified in CYP450 enzyme with RRLC-MS/MS. The difference between the experimental group and control group was not significant except CYP1A2 group, indicating that ginsenoside Rb1 has more induced effect to the CYP1A2 group than the others. Ginsenoside Rb1 promoted reaction and speed up the metabolism of probe drug. The method can effectively and easily analyze the impact on the enzyme and possible metabolites.

    WST-8 Assay for Living Cell Viability Detection by Surface-enhanced Raman Spectroscopy
    YANG Jin, LIU Zhuo, WANG Xiaohui, SUI Huimin, MAO Zhu, ZHAO Bing
    2015, 36(10):  1900-1905.  doi:10.7503/cjcu20150282
    Asbtract ( )   HTML ( )   PDF (3313KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Surface-enhanced Raman scattering(SERS) technique was used to develop and optimize a novel and quantitative 2-(2-methoxy-4-nitrophenyl)-3-(4-nitrophenyl)-5-(2,4-disulfophenyl)-2H-tetrazolium monosodium salt(WST-8) assay for living cell viability. The influences of pH and dosage of reductant nicoti-namide adenine dinucleotide(NADH) on WST-8 formazan signal were examined. SERS signals of formazan with high resolution and great diversity between WST-8 and formazan were observed in neutral conditions. Meanwhile, the signals of formazan(560, 1351, 1598, 1616 cm-1) could be found clearly when the concentration of NADH was four times that of WST-8. Compared with the traditional method, this assay appears higher sensitivity and selectivity for WST-8 formazan. Moreover, the detection limit of formazan is as low as 10 μmol/L.

    Spectral Performance and Fluorescence Detection of Ionic Liquid [MBPy]Tf2N
    OUYANG Qiaofeng, ZHENG Lanlan, CAO Hong, ZHANG Xin, LI Chun, SHEN Jiao, CHEN Liting, LIU Jin
    2015, 36(10):  1906-1911.  doi:10.7503/cjcu20150242
    Asbtract ( )   HTML ( )   PDF (1401KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    The detection method of hydrophobic ionic liquid N-methyl-N-butyl pyrrolidinium bis[(trifluoro-methyl)sulfonyl]imide([MBPy]Tf2N) was established by means of fluorescence spectrum and applied for the analysis of [MBPy]Tf2N from glycyrrhizin biological catalysis system containing ionic liquid. The effects of solvent, ethanol-water mixture solvent and pH on fluorescence spectrum were explored. Spectral features of [MBPy]Tf2N, the maximum absorption wavelength at 186 nm, were apparently cannot detect [MBPy]Tf2N by common UV method. The maximum excitation wavelength of [MBPy]Tf2N is at 228 nm and the maximum emission wavelength of it is at 340 nm, which can well againsted photobleaching and the fluorescence quantum yield was 0.067 in water. The fluorescence intensity increased in ethanol-water mixture solvent and changed much in alkaline medium. The fluorescence detection method for [MBPy]Tf2N had a wide linear range over [MBPy]Tf2N concentration from 5.00 to 1.25×103 μg/mL with a detection limit of 1.00 μg/mL(S/N=3). The spiked recoveries were from 97.4% to 107.4%(RSD=4.6%) in glycyrrhizin biological catalysis system.

    Direct Analysis of Navel Orange Using Internal Extractive Electrospray Ionization Mass Spectrometry
    LU Haiyan, ZHANG Hua, ZHOU Peng, YANG Meiling, ZHONG Tao, YAO Guocan, CHEN Huanwen
    2015, 36(10):  1912-1918.  doi:10.7503/cjcu20150233
    Asbtract ( )   HTML ( )   PDF (2199KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Internal extractive electrospary ionization mass spectrometry(iEESI-MS) was applied on the assessment of navel orange quality without any sample pretreatment. Both endocarp tissues(72 samples) and flesh tissues(72 samples) of navel oranges from three habitats were interrogated directly by iEESI-MS at mass range of m/z 50—2000. A fused silicon capillary was inserted into the navel orange tissue, allowing a distance of 2 mm between the fused silicon capillary tip and the sample apex. The apex of the sample was pointed to the mass spectrometer ion inlet intentionally with a distance of 4—5 mm. Extraction solvent biased with a high voltage(4.5 kV) was injected through the fused silicon capillary into the navel orange tissue at a flow rate of 2 μL/min, producing charged fine droplets containing chemicals toward the adjacent mass spectrometer inlet. Chemical constituents such as sugars, amino acids, vitamin and alkaloids were simultaneously extracted from the navel orange tissue, and identified through collision-induced dissociation(CID) experiment. Furthermore, mass spectral fingerprints were processed by principal component analysis(PCA) to visualize the quality differences. Our experimental results indicated that iEESI-MS can directly characterize the quality differences of navel oranges by molecular analysis. The merits of iEESI-MS include simplicity, good specificity, high throughput and minimum sample pretreatment.

    Organic Chemistry
    Assembly and Property of Rotaxane Based on Cucurbit[6, 7]urils Host and Two Kinds of N,N'-Phthalimide Appended 4,4'-Dipyridyl Terminated Viologen Guest
    CHEN Shiyan, CUI Xiaowei, WANG Chuanzeng, NI Xinlong, MA Peihua, ZHANG Jianxin
    2015, 36(10):  1919-1823.  doi:10.7503/cjcu20150438
    Asbtract ( )   HTML ( )   PDF (1345KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Two guests based on N,N'-phthalimide substituted 4,4'-dipyridyl with different alkyl chain lengths were synthesized(G1 and G2). The supramolecular self-assemblies of G1 and G2 with cucurbit[6]uril(Q[6]) and cucurbit[7]uril(Q[7]) were evaluated by UV-Vis spectra, hydrogen nuclear magnetic resonance(1H NMR) and isothermal titration calorimetry(ITC). The experiment results suggested that [2]rotaxane can be only formed between G1 and Q[6] in boiling aqueous solution by slipping. On the contrary, [2]pseudorotaxane can be easily formed between Q[7] and G1 or G2 in aqueous solution at room temperature.

    Synthesis, Crystal Structure and Spectral Properties of Six Indole Dimethine Cyanines as Well as Their Biological Application
    ZHANG Jianghua, LÜ Ying, JIA Hongliang, SONG Yinyin, SUN Xiaoxia, CHAI Dunxiao, WANG Lanying
    2015, 36(10):  1924-1932.  doi:10.7503/cjcu20150128
    Asbtract ( )   HTML ( )   PDF (2323KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Six novel bis(N-alkyl) indole dimethine cyanine dyes(C1—C6) were synthesized using heterocyclic quaternary ammonium salts with active methyl and N-methyl-3-indole formaldehyde as starting materials and piperidine as catalyst. The dyes were identified by UV-Vis, 1H NMR, IR and HRMS and the crystal structures of dyes C1 and C5 were determined by X-ray single crystal diffraction analyzer. The investigation of the spectral properties of dyes C1—C6 in different solvents showed that the maximum absorption wavelength of the dyes was in the range of 370.0—521.0 nm, the emission wavelength was located in 466.4—600.8 nm and the molar extinction coefficients was in the range of 0.80×104—3.92×104 L·mol-1·cm-1 in different solvents. The interactions of dyes C1—C6 with DNA, bovine serum albumin(BSA), muramidase, amylase, bovine hemoglobin and chymotrypsin were investigated, respectively. The results showed that the spectral properties of dyes C3, C4 and C5 were significantly changed with the addition of DNA and the quantum yields of the dyes were increased with the increase of DNA concentration. The investigation of the cytotoxicity and cell staining of the selected dyes C5 and C6 showed that the two dyes had virtually no toxicity at applications dose and time and could stain cell nucleus, suggesting that the dyes C5 and C6 could be used as potential fluorescent reagents to observe living cells.

    Physical Chemistry
    Fabrication and Characterization of (Hydroxyl camptothecin@sodium cholate)-layered Double Hydroxide Nanohybrids
    PANG Xiujiang, LIU Yuan, CHEN Li, QUAN Zhenlan
    2015, 36(10):  1933-1938.  doi:10.7503/cjcu20150353
    Asbtract ( )   HTML ( )   PDF (2016KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    (Hydroxyl camptothecin@sodium cholate)-layered double hydroxide(LDH) nanohybrids were prepared by a modified drug-coassembly method. Firstly, Hydroxyl camptothecin(HCPT) was incorporated into micelles derived from sodium cholate(SCL) which negatively charged. The negatively charged micelles intercalated HCPT@SCL-LDH nanohybrids were prepared by a co-assembly between LDH nanosheets and sodium cholate micelles with the encapsulated HCPT could keep the biological active lactone form, and the drug loading of so-obtained nanohybrid was 12.9%.(HCPT@SCL)-LDH was modified using polyethylene glycol(PEG) and carboxymethylcellulose(CMC), respectively. The results showed that the dispersity of nanohybrids was obviously improved, and PEG worked better than CMC. The PEG-(HCPT@SCL)-LDH had favorable dispersity with average size of ca. 70 nm. PEG-(HCPT@SCL)-LDH showed well controlled release property and in vitro drug release kine-tics from the nanohybrids could be fitted with the pseudo-second-order kinetic model. The diffusion of HCPT through the LDH particles played an important role in controlling the drug release.

    Theoretical Study on the Binary Phase Diagrams of the Zr-X (X=Li, Na, K, Sc, Hf) Systems
    HU Biao, ZHOU Peng, PAN Chengling, DU Yong, LIU Shuhong, LI Yiwei, HAN Jiangjun
    2015, 36(10):  1939-1944.  doi:10.7503/cjcu20150345
    Asbtract ( )   HTML ( )   PDF (1545KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    The Zr-X(X=Li, Na, K, Sc, Hf) systems were studied with the calculation of phase diagrams(CALPHAD) approach. A set of the thermodynamic parameters of the liquid, (αZr), (βZr), (Li), (Na), (K), (αSc), (βSc), (αHf) and (βHf) phases was obtained based on the critical review of the available experimental data. The gas phase for the three binary systems, i.e. Zr-Li, Zr-Na and Zr-K, was treated with the ideal gas model. Comparisons between the calculated and measured phase diagrams show that the experimental phase equilibria information is satisfactorily accounted for by the present thermodynamic description.

    Density Functional Theory Investigation on the Effect of Alkali Metal Cations on the Catalytic Performance for Cu+Y Zeolites in Oxidative Carbonylation of Methanol
    ZHANG Yanqing, ZHENG Huayan, ZHANG Riguang, LI Zhong, WANG Baojun, ZHAO Qiuyong
    2015, 36(10):  1945-1953.  doi:10.7503/cjcu20150327
    Asbtract ( )   HTML ( )   PDF (4013KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    On the basis of density functional theory, influence of co-cations(M=Li+, Na+, K+, Rb+)adjacenting active center Cu+ on the electronic properties and catalytic activity of Cu+Y zeolites in oxidative carbonylation of methanol to dimethyl carbonate was investigated. CuMY stable configurations were constructed, CO insertion CH3O species to CH3OCO was used to evaluate the catalytic activity of CuY zeolites, due to the fact that it was the rate-limiting step of oxidative carbonylation of methanol. The calculation results indicate that Li+, Na+, K+ cations can locate site Ⅰ' in small cages of Y zeolites surrounding the active center Cu+, the adsorption energy of CH3OH, CO, CH3O and co-adsorbed CO/CH3O on CuMY zeolite increases gradually with increase of cation size, the stability of transition states for CO insert into CH3O reaction comes to decrease, increases the activation barriers and the corresponding catalytic performance declines. Whereas, Rb+ and Cs+ cations located Ⅱ* in the supercage as increase in cation size, decreases activation energy for CO insertion reaction, improves the stability of transition states and the catalytic activity of CuY zeolites. The order of catalytic activity of CuMY zeolites is CuLiY-Ⅰ'>CuCsY-Ⅱ*>CuNaY-Ⅰ'>CuRbY-Ⅱ*>CuKY-Ⅰ'>CuCuY-Ⅰ'. The CuLiY-Ⅰ' catalyst exhibits the best catalytic performance with a lowest rate-limiting reaction activation barrier of 52.74 kJ/mol.

    Density Functional Theory Studies on the t-Butoxyl Radical Mediated Hydrogen Atom Transfer Reactions
    LI Yue, FANG Decai
    2015, 36(10):  1954-1960.  doi:10.7503/cjcu20150326
    Asbtract ( )   HTML ( )   PDF (2991KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    The reaction mechanisms of hydrogen abstractions from carbon by the t-butoxyl radical were investigated with several density functional theory(DFT) methods, such as CAM-B3LYP, M062x and wB97x. The results show that most of these reactions are dominated more by entropic than by enthalpic factor. The activation free energy barriers were calculated with both gas-phase translational entropy and solution translational entropy, in which those from ideal gas-phase translational entropy(output of Gaussian job) were much higher than the experimental estimations. It has been verified that free-energy barriers of amines and hydrocarbons reactions generated from solution translational entropies are close to the experimental measurements, but all these methods predict a little low free-energy barriers for alcohols and ethers reactions.

    Electrocatalytic Performance of Highly Loaded PtNi Intermetallic Nanoparticles for Oxygen Reduction
    HUANG Qinghong, ZOU Liangliang, ZHOU Yi, ZOU Zhiqing, ZHANG Xiaogang, YANG Hui
    2015, 36(10):  1961-1968.  doi:10.7503/cjcu20150303
    Asbtract ( )   HTML ( )   PDF (4943KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    PtNi/C disordered alloy nanoparticles, synthesized in ethylene glycol solution, were annealed and converted into ordered PtNi/C intermetallic nanoparticles. Such an ordered intermetallic PtNi/C catalyst showed enhanced specific activity and mass activity, which were about 2.3 and 1.66 times those of Pt/C for the oxygen reduction reaction(ORR), in comparison with the Pt/C catalyst. After accelerated stress tests(ASTs), the ORR mass activity of the Pt/C and PtNi/C intermetallic nanoparticles decreased to 88.92% and 36.95% of the initial values, respectively; and the mass activity of PtNi/C intermetallic nanoparticles after ASTs was equivalent to the initial one of the Pt/C catalyst. The enhanced ORR activity and durability of the PtNi/C intermetallic nanoparticles could be attributed to the ordered atomic configuration and the increased content of zero valence metal on the surface of nanoparticles. Moreover, the ordered PtNi/C intermetallic nanoparticles exhibited higher methanol tolerance during the ORR than the Pt/C catalyst.

    Particle Size Effect of Ru-Zn Catalysts on Selective Hydrogenation of Benzene to Cyclohexene
    SUN Haijie, CHEN Lingxia, HUANG Zhenxu, LIU Shouchang, LIU Zhongyi
    2015, 36(10):  1969-1976.  doi:10.7503/cjcu20150288
    Asbtract ( )   HTML ( )   PDF (4377KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Ru-Zn catalysts modified by water soluble polymers were prepared by a precipitation method. The catalysts after hydrogenation were characterized by X-ray diffraction, transmission electron microscopy, energy dispersive spectroscopy, X-ray photoelectron spectroscopy and N2 physisorption. It was found that the type of water-soluble polymers and the dosage of PEG-20000 imposed a remarkable effect on the particle size of Ru. With the Ru particle size in Ru-Zn catalysts increasing, benzene conversion decreased, and the maximum cyclohexene yield showed a volcanic-type variation tendency. When the Ru particle size of the Ru-Zn catalyst modified by 0.4 g PEG[m(PEG-20000)∶m(Ru)=0.2] was 4.8 nm, a maximum cyclohexene yield of 62.2% was obtained on this catalyst. The Ru particle size could produce an effect on the Zn/Ru atomic ratio on the catalyst surface, which was the primary reason why the Ru particle size could affect the performance of Ru-Zn catalysts.

    Photocatalytic Performances for Mixed-phase Hierarchical Structure TiO2 Prepared by Physical Mixing
    ZHANG Xiao, XIE Yingjuan, MA Peijun, WU Zhijiao, ZHAO Suling, PIAO Lingyu
    2015, 36(10):  1977-1983.  doi:10.7503/cjcu20150287
    Asbtract ( )   HTML ( )   PDF (5048KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Mixed-phase hierarchical structure titania(MH-TiO2) with different rutile contents were synthesized via physically mixing hierarchical flower-like anatase TiO2 and rutile TiO2 nanoparticles. The morphology, phase-structure and properties of the samples were studied via scanning electron microscopy(SEM), transmission electron microscopy(TEM), X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS) and UV-Vis diffused reflectance spectrometry(UV-Vis DRS). The photocatalytic activity of MH-TiO2 for degradation of methylene blue under ultraviolet light irradiation was investigated. The results indicate that the hierarchical structure can enlarge specific surface area thus ensuring the effective adsorption of reactant and improving the utilization of light. What’s more, heterojunction structure can increase the separation efficiency of the photogenerated electrons and holes and improve the photocatalytic performances of the material.

    Preparation and Photocatalytic Activity of Fe-Doped Hydroxyl-Zr Pillared Titanate
    HE Liwen, LIN Bizhou, ZHANG Guohua, YAO Qianru
    2015, 36(10):  1984-1989.  doi:10.7503/cjcu20150280
    Asbtract ( )   HTML ( )   PDF (2755KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    To fabricate Fe-doped-hydroxyl-Zr pillared titanate(abbreviated as FZPT) with delaminated structure, the exfoliated layered titanate in aqueous solution was reassembled in the presence of hydroxyl-Zr oligocations and iron cation under the exfoliation-restacking route to induce a great number of mesopores and eventually a large surface area of photocatalysts. The influence of doping iron cations on the preparation and catalytic activity of the Zr-pillared composites(ZPT) was investigated. The material was characterized by powder X-ray diffraction, UV-Vis DRS spectra, scanning electron microscopy(SEM), transmission electron microscopy(TEM), and specific surface area and porosity measurements. When n(Fe)/n(Zr) in FZPT was less than 10%, the diameter of mesopore and specific surface area increased with the amount of iron, and vice versa. The results of degradation of methylene blue(MB) under ultraviolet and visible radiation showed that the FZPT nanocomposites exhibited higher photocatalytic activities than ZPT, which was based on the mesoporous structure and increased specific surface area. The FZPT-0.20 nanocomposite exhibited an enhanced photocatalytic activity in the degradation of MB under visible-light irradiation, attributed to the electronic coupling between the host and the guest cations contained iron.

    MoO2/C Co-coated Si/graphite Composite as Anode Materials for Lithium Ion Batteries
    YIN Hong, ZHOU Dan, CONG Lina, XIE Haiming, QIU Yongqing
    2015, 36(10):  1990-1994.  doi:10.7503/cjcu20150241
    Asbtract ( )   HTML ( )   PDF (4111KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    A sol-gel method was used to fabricate MoO2 and C co-coated Si/graphite particles to form Si/graphite/MoO2/carbon(SGMC) composite as anode materials for lithium ion batteries. X-ray diffraction(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), cyclic voltammetry(CV) and electrochemical impedance spectroscopy(EIS) were utilized to characterize the morphology and properties of the composite. The MoO2/C double coating has inhibited the volume expansion, improved the electronic conductivity and lithium ion mobility, and further improved the electrochemical performances. Electrochemical tests showed that the first charge capacities of SGMC composite was 2494 mA·h/g with an initial coulombic efficiency of 72%. The charge capacity maintained 636.6 mA·h/g over 100 cycles.

    Excited State Dynamics of γ-Crotonolactone: Resonance Raman Spectroscopy and Complete Active Space Self-consistent Field(CASSCF) Study
    OUYANG Bing, XUE Jiadan, ZHENG Xuming
    2015, 36(10):  1995-2001.  doi:10.7503/cjcu20150226
    Asbtract ( )   HTML ( )   PDF (2426KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    The structural dynamics and decay mechanisms of γ-crotonolactone in the light-absorbing S2 excited states were studied by resonance Raman spectroscopy and complete active space self-consistent field(CASSCF) computations. The electronic spectra assignments and the vibrational assignments were done on the basis of the density-functional theory computations and the results of corresponding spectra. The resonance Raman spectra at four excitation wavelength which covered A-band were obtained. CASSCF method was carried out to determine the minimal excitation energies and excited geometries of S1,min, S2,min, T1,min, T2,min, T3,min, as well as some conical intersection points. The relation between the structures of excited state S2,minas well as internal conversion point CI(S2/S1) and the intensity mode of resonance Raman spectra was studied. The efficiency of various intersystem crossing is evaluated on the basis of the El-Sayed’s rule, and two major decay channels from S2,FC to ground state S0 were proposed. One is the internal conversion channel and the other is the intersystem crossing channel.

    Theoretical Investigation on the Effect of Extra Donor on the Performance of D-π-A Sensitizer in Dye-sensitized Solar Cell
    WU Shuixing, ZHANG Jianzhao, SU Xin, ZHANG Ji, WU Yong, GENG Yun, SU Zhongmin
    2015, 36(10):  2002-2008.  doi:10.7503/cjcu20150214
    Asbtract ( )   HTML ( )   PDF (1522KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    In order to explore the effect of extra donor on the performance of sensitizer in dye-sensitized solar cell(DSSC), we have analysized geometrical and electronic structures, absorption spectra, electrochemical properties, charge recombination and conduction band shift for four dyes based on density functional theory(DFT) and time-dependent density functional theory(TD-DFT) calculations. The results show that compared with the classical D-π-A sensitizer 1, although the introduction of extra donor has no significant effect on the conduction band shift, it could change the degree of molecular conjugation and increase their molar absorption coefficients. Importantly, the introduction of extra donors could increase significantly the dye cation hole-conduction surface distance, and thus reduce the charge recombination between the injected electron and dye cation. The introduction of extra donors also make I2 locate at the outside of sensitizer, thus lower the recombination rate between the injected electron and electrolyte. We hope our calculations could provide a clear strategy for experimental synthesis of high performance dyes.

    Synthesis and Surface Properties of Siloxane Gemini Imidazolium Surfactant
    LIANG Weiping, ZHAO Xiaohui, AN Dong, XU Qian, YE Zhiwen
    2015, 36(10):  2009-2015.  doi:10.7503/cjcu20150207
    Asbtract ( )   HTML ( )   PDF (1769KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    A new siloxane gemini imidazolium surfactant 3,3'-di[γ-tri(trimethylsiloxy)silyl]propylchloride-1,1'-(1,4-butanediyl)-bisimidazole([Si4-4-Si4im]Cl2) was synthesized with chlorotrimethylsilane, γ-chloropropyltrichlorosilane, 1,4-dichlorobutane and imidazole. The structure of the surfactant was characte-rized by MS and 1H NMR spectra, and the results proved that it was consistent with the target structure. The surface tension of the surfactant was measured by Wilhelmy measuring plate method at 25 ℃. It indicates that the γcmc of the surfactant in aqueous solution can be reduced to 18.6 mN/m and the value of cmc is 0.54 mmol/L. The thermodynamic parameters of micellization(ΔGm 0,ΔHm 0,ΔSm 0) of the surfactant were researched by determination of the electrical conductivity in different concentrations. The results suggest that the process of micellization is spontaneous and micellization of [Si4-4-Si4im]Cl2 is entropydriven at 15—35 ℃.

    Preparation and Oxygen Reduction Catalytic Performance of Iron-phthalocyanine Polymer/Multi-walled Carbon Nanotubes Composites
    LI Zhipan, PENG Yingxiang, YANG Shifeng, ZHANG Rui, LI Kai, ZUO Xia
    2015, 36(10):  2016-2023.  doi:10.7503/cjcu20150121
    Asbtract ( )   HTML ( )   PDF (3362KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Four iron-phthalocyanine polymers/multi-walled carbon nanotubes(Poly-FePc/MWCNTs) composites were sythetized by an efficient and facile microwave method. The ultraviolet-visible(UV-Vis) spectroscopy and transmission electron microscopy(TEM) results showed that the iron-phthalocyanine polymers had uniformly loaded onto the MWCNTs. The oxygen reduction reaction activity of Poly-FePc/MWCNTs was measured by linear sweep voltammetry(LSV) and electrochemical impedance spectrometry(EIS), the results demonstrated that FePPc/MWCNTs exhibited the best oxygen reduction catalytic activity. Finally, the relationship between the electrocatalytic activity and molecular structures of Poly-FePc/MWCNTs was revealed by X-ray photoelectron spectroscopy(XPS) and X-ray absorption fine spectroscopy(XAFS). The results showed that if Fe-N4 in FePPc/MWCNTs presents a square planar structure, it could improve the synergistic effect between the iron-phthalocyanine polymers and the MWCNTs. As a consequence, it can accelerate the electrons transfer and enhance the oxygen reduction catalytic activity of the composite.

    Polymer Chemistry
    Preparation and Characterization of TiO2 Nanorods/SiO2@TiO2 Core Shell Particles and Its Application in PLLA
    LI Gen, WANG Rui, WANG Feng, LIANG Ningning, ZHU Zhiguo, ZHANG Xiuqin, YANG Mingshu
    2015, 36(10):  2024-2033.  doi:10.7503/cjcu20150555
    Asbtract ( )   HTML ( )   PDF (6373KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Rutile-type titanium dioxide(TiO2) nanorods were synthesized using titanium trichloride as titanium source, which were further superficially modified by tetraethoxysilane and the nano-TiO2 coated by SiO2 were obtained(SiO2@TiO2). The average length of TiO2 nanorods is about 50 nm, the average diameter of TiO2 nanorods is about 8 nm and the thickness of the SiO2 coating layer is about 4 nm. The maximum absorption wavelength of SiO2@TiO2 has a slight blue shift compared with that of TiO2. Poly(L-lactic acid)(PLLA)/(SiO2@TiO2) nanocomposites were prepared by melt blending. The thermal, crystallization, UV-shielding and stretching properties of PLLA and PLLA/(SiO2@TiO2) nanocomposites were characterized by transmission electron microscope(TEM), thermogravimetric analysis(TGA), differential scanning calorimetry analysis(DSC), ultraviolet-visible absorption spectrometry(UV-Vis) and wide angle X-ray scattering(2D-WAXS). The results showed that the SiO2@TiO2 nanoparticles were dispersed well in the PLLA matrix. SiO2@TiO2 improved the thermal decomposition temperature and crystallization rate of PLLA and had a heterogeneous nucleation role in PLLA. The PLLA/(SiO2@TiO2) films had excellent UV shielding property while maintaining high visible transmittance. The orientation and crystallinity of PLLA/(SiO2@TiO2) nanocomposites stretched at 90 and 100 ℃ were higher than that of PLLA.

    States of Water in Cellulose Hydrogels and Influence on the Crystallization of Cellulose
    CHEN Feng, LIU Zhengying, HUA Sun, KAN Ze, YANG Mingbo
    2015, 36(10):  2034-2039.  doi:10.7503/cjcu20150528
    Asbtract ( )   HTML ( )   PDF (5885KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    A study inspired by biosynthesis of cellulose in higher plant was made on an attempt to investigate the state of water in cellulose hydrogels and its influence on the crystallization of cellulose. The differential scanning calorimetry(DSC) results indicate that there are 3 types of water in cellulose hydrogels: nonfreezing water, freezing bound water and free water. The ratio of the nonfreezing water to dry cellulose in the hydrogels is about 1.6 g/g, 5 times more than the adsorbed water in dry cellulose. In such a highly hydrated state, the aggregation and crystallization of cellulose are inhibited, the lower the water content, the completer the crystallization of cellulose, which is characterized by X-ray diffraction(XRD), polarizing optical microscope(POM) and scanning electron microscopy(SEM). It is suggested that the little inhibition effect of nonfreezing water on the crystallization is due to the instability of the hydrogen bond between the water and cellulose. The results demonstrate the high content of nonfreezing water in cellulose hydrogels.

    Oxidized Cellulose Enhanced Collagen Hydrogels
    ZHANG Xia, ZHOU Hao, YANG Yuhong, HUANG Yufang, CHEN Xin
    2015, 36(10):  2040-2046.  doi:10.7503/cjcu20150520
    Asbtract ( )   HTML ( )   PDF (4230KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Aldehyde-functionalized cellulose(DAC) was obtained by the oxidization of cellulose, and was applied as a macromolecular crosslinker to modify the collagen(Col) hydrogel. The structures and properties of oxidized cellulose modified collagen(Col/DAC) hydrogels were characterized with SEM observation, mechanical test and rheology analysis. The results show that the mechanical properties and thermal stability of Col/DAC hydrogels are significantly improved compared to the pristine Col hydrogel, especially the breaking compression strength of Col/DAC hydrogel can be more than one order of magnitude higher than the pristine Col hydrogel. In addition, it is shown that introducing of oxidized cellulose does not bring the cytotoxicity that is often seen from the conventional chemical crosslinking method, and maintains the good biocompatibility of the final product. Therefore, such a biocompatible and strong collagen hydrogel obtained from the oxidized cellulose modification may have the great potential in tissue engineering and other biomedical fields.

    Preparation of a Polymer Containing Sprio-dioxolane Based on Phenanthrene Block via in situ Reaction and Its Photo-electro Properties
    WANG Zhiming, WANG Jing, HOU Xue, ZHANG Xiaojuan, LU Ping
    2015, 36(10):  2047-2052.  doi:10.7503/cjcu20150480
    Asbtract ( )   HTML ( )   PDF (1868KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    The reaction between carbonyl group in ketone or aldehyde and glycol is a class protection reaction in organic chemistry, and usually, the sprio-dioxolane structure was inserted to the original framework. In this work, the high-efficiency reaction was used between a kind of reactive polymer(L-PPQF) and glycol, because of the existence of reactive position in phenanthrenequinone block due to its ortho-carbonyl structure. A novel polymer containing sprio-dioxolane based on phenanthrene block was prepared by in situ reaction, and named L-PPOF. Collecting the results of NMR, MS and elemental analysis from the model oligomer(L-DFPQ) of L-PPQF and its product after in situ reaction, this new heterocyclic structure was confirmed. The polymer structure was also clear after chartering by the measurement in further such as NMR and FTIR. The data of photo-physical and electrochemistry show that, the newborn polymer containing sprio-dioxolane modified phenanthrene unit exhibited higher fluorescence quantum efficiency in solution and solid, more suitable electron-injection energy level than its matrix polymer L-PPQF or PF. The primary OLED performance implied the L-PPOF had good potential value.

    Synthesis and Characterization of Electro-optic Materials Based on Intermolecular Lateral Hydrogen Bonding
    ZHANG Qingzhong, ZHANG Junmei, LIU Yuping, REN Xiao, HUANG Wei
    2015, 36(10):  2053-2060.  doi:10.7503/cjcu20150402
    Asbtract ( )   HTML ( )   PDF (2225KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    A new series of azobenzene nonlinear optical(NLO) chromophores was prepared by diazo coupling and esterification reactions, and the “gest-host” and “supramolecular” NLO materials were also prepared by doping or intermolecular lateral hydrogen bonding interaction. The chemical structures of these chromophores were characterized. The intermolecular lateral hydrogen bonding interaction in these chromophores was confirmed by 1H NMR. The UV-Vis spectra of these NLO materials showed that the chromophore loading, poling efficiency and alignment stability could be greatly improved by the intermolecular lateral hydrogen bonding interaction. The electro-optic(E-O) activities of these materials were also studied. Compared with “gest-host” type, the “supramolecular” type NLO materials based on the intermolecular lateral hydrogen bonding interaction had larger E-O coefficients.

    Synthetic of PGMA-EDA-g-PEG-g-DS@IO as a Magnetic Resonance Contrast Agent for Atherosclerosis
    HU Qi, FANG Chao, ZHAO Wai’ou, LI Yapeng, CHEN Xia, WANG Jingyuan
    2015, 36(10):  2061-2066.  doi:10.7503/cjcu20150391
    Asbtract ( )   HTML ( )   PDF (2754KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    To design a new magnetic resonance(MR) imaging contrast agent of atherosclerosis, poly(glycidyl methacrylate)-graft-ethane diamine(PGMA-g-EDA) was prepared by the ring-opening reaction of PGMA which was synthesized by atom transfer radical polymerization(ATRP). Poly-ethylene glycol(PEG) and dextran sulfate(DS) were graft modified to PGMA-g-EDA continuously via amidation reaction and reductive amination to synthesis PGMA-EDA-g-PEG-g-DS. The structure and properties of PGMA-EDA-g-PEG-g-DS were characterized through nuclear magnetic resonance(1H NMR). Fourier transform infrared spectroscopy(FTIR) and gel permeation chromatography(GPC). The superparamagnetic iron oxide nanoparticles(IONPs) were coated with PGMA-EDA-g-PEG-g-DS by ligand exchange to prepare water-soluble IO. The transmission electron microscopy(TEM) analysis indicated that micelles were well dispersed in water and had uniform sizes. The result of thermogravimetric analysis(TGA) indicated that about 70%(mass fraction) polymers coated on the surface of IO. The cell counting kit(CCK) assay showed no significant toxicity to RAW264.7. The above results confirm that PGMA-EDA-g-PEG-g-DS@IO can be used as a potential contrast agent for atherosclerosis MR imaging.

    RAFT Polymerization of Acrylamide Polyhedral Oligometic Silsesquioxane in Supercritical CO2+
    CHENG Long, BIAN Zhongxuan, DING Minyuan, ZHAO Meng, LI Hui
    2015, 36(10):  2067-2072.  doi:10.7503/cjcu20150377
    Asbtract ( )   HTML ( )   PDF (1207KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Polyacrylamide(PAM) isobutyl-polyhedral oligometic silsesquioxane(POSS)(PAMPOSS) homopolymer and PAMPOSS-b-PMMA(polymethyl methacrylate) block copolymers were prepared via reversible addition-fragmentation transfer(RAFT) polymerization using benzenecarbodithioic acid 1,1-dimethylethyl ester as the RAFT agent in supercritical CO2. The products were characterized. The results show that polymerization reaction in supercritical CO2 is well controlleded. Both of PAMPOSS and PAMPOSS-b-PMMA have high degree of polymerization(DP) and low polydispersity index(PDI). It can be also found that the polymerization of AM-POSS is a homogeneous reaction, and the solubility of POSS containing polymers in supercritical CO2 is effected by the crystallinity of POSS.

    Synthesis and Properties of Melt Processable Acrylonitrile-N-vinylimidazole Copolymers and Fiber
    HAN Na, LI Huihui, LI Chuanbao, ZHANG Xingxiang, LI Wei, WANG Dong
    2015, 36(10):  2073-2080.  doi:10.7503/cjcu20150309
    Asbtract ( )   HTML ( )   PDF (3368KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Polyacrylonitrile(PAN) and acrylonitrile(AN)-N-vinylimidazole(VIM) copolymers[abbreviated as P(AN-co-VIM)] with various n(AN)∶n(VIM)(93∶7—80∶20) were synthesized by free-radical solution copolymerization in dimethyl formamide(DMF). The P(AN-co-VIM) copolymers(82∶18 and 80∶20) possessed good melt processability, which were melt spun at the temperature of 210—220 ℃. The crystallinity, thermodynamics behavior and the composition of P(AN-co-VIM) copolymers were studied and characterized by ubbelodhe viscosimeter, Fourier transform infrared spectroscopy(FTIR), nuclear magnetic resonance(1H NMR), differential scanning calorimetry(DSC), X-ray diffraction(XRD) analyses and hot stage microscope. The results revealed that P(AN-co-VIM) could be synthesized successfully by free-radical solution copolymerization. P(AN-co-VIM) could be melt processable as VIM molar fraction is higher than 10%. The melting temperature of P(AN-co-VIM) shifts continuously to the lower temperature with the comonomer contents increasing. When the molar fraction of VIM is increased to 20%, the melting point of P(AN-co-VIM) copolymer reduced from 317 ℃ to 180 ℃. The highest decomposition temperature is 313.7 ℃. The apparent morphology and mechanical properties of the P(AN-co-VIM) fibers were characterized by scanning electron microscope(SEM) and single fiber electronic tensile strength test. The results show that the fibers have smooth surface and compact cross section. As-spun P(AN-co-VIM) fiber gets the fracture strength of 1.58 cN/dtex and the elongation at break attained 11.2%. After post-treatment, the fiber is expected to be widely used in the field of carbon fiber.