Table of Content

10 September 2013, Volume 34 Issue 9

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Content

Cover and Content of Chemical Journal of Chinese Universities Vol.34 No.9(2013)

2013, 34(9):  0-0. 

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Review

Recent Progress in Preparation and Application of Organic-silica Hybrid Monolithic Columns

ZHANG Zhen-Bin, OU Jun-Jie, LIN Hui, LIU Zhong-Shan, DONG Jing, ZOU Han-Fa

2013, 34(9):  2011-2019.  doi:10.7503/cjcu20130590

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In recent years, the organic-silica hybrid monolith has drawn more and more attention since it combines the advantages of the organic polymer monolith and the silica monolith in easy preparation, high mechanical strength, and good permeability, etc. The methods for preparation of organic-silica hybrid monolithic columns mainly include conventional sol-gel method, one pot method and other polymerization methods. Currently, the hybrid monolithic columns were widely applied in nano and micro scale separation and analysis, sample pretreatment and the matrix for immobilized enzyme microreactor, etc. This article reviews the recent progress in preparation and application of organic-silica hybrid monolithic columns, and prospects its development in the future.



Overview of Graphene/Polyaniline Composite for High-performance Supercapacitor

CHEN Zhong-Xin, LU Hong-Bin

2013, 34(9):  2020-2033.  doi:10.7503/cjcu20130517

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Polyaniline(PANI) is one of the most intriguing conducting polymers with ultrahigh specific capa-citance. The synergistic effect between PANI and graphene nanosheets(GN) could remarkably diminish their inherent drawbacks, and enhance the capacitance/cycling life of GN-PANI supercapacitors. We review the recent advances in this regard, discuss the effect of synthetic routes used and surface functionalization of GN on the performance of GN-PANI supercapacitor electrodes, and highlight the importance of fabricating hierarchical structure and 3D porous networks.



Letter

Back Incident Au/TiO₂/Au Schottky Junction Ultraviolet Detector

LIU Guo-Hua, GU Xue-Hui, LI Hai-Long, GUO Wen-Bin, ZHANG Xin-Dong

2013, 34(9):  2034-2036.  doi:10.7503/cjcu20130612

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Rutile phase TiO₂ nanowire arrays were prepared on F:SnO₂(FTO) substrate via a low temperature hydrothermal method and characterized by means of X-ray diffraction(XRD) and scanning electron microscopy(SEM). Then back incident ultraviolet photodetectors of Au/TiO₂/Au structure were fabricated by traditional photo-lithography technique and magnetron sputter plating. At 2.0 V bias, a very low dark current of 3.5 nA is achieved due to the back-to-back structure of the device. Under the irradiation of 360 nm UV-light, the photocurrent can reach 704 nA. The maximum responsibility is up to 0.162 A/W at 360 nm, corresponding to a quantum efficiency of 56.2%.



Cellulose Ester/Ionic Liquids Composite Membranes for CO₂-Favored Permeation

CHEN Jing, ZHANG Jin-Ming, ZHANG Jun

2013, 34(9):  2037-2039.  doi:10.7503/cjcu20130480

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A novel cellulose ester grafted ionic liquid(IL) copolymer, 1-vinyl-3-butylimidazolium tetra-fluoroborate(VbimBF₄) grafted cellulose butyrate acrylate(CBA)(CBA-g-VbimBF₄) was synthesized by free radical graft copolymerization. The CBA-g-VbimBF₄ membranes exhibited improved CO₂ permeability over the conventional cellulose acetates. Furthermore, four kinds of ILs, EmimBF₄, BmimTf₂N, BmimAc and EmimAc were incorporated into CBA-g-VbimBF₄ copolymer, and obtained CBA-g-VbimBF₄/ILs composite membranes exhibited both high permeability and permselectivity for CO₂.



Article: Inorganic Chemistry

Hydrothermal Syntheses and Characterization of Two Multi-vanadium Capped Keggin Polyoxoniobates Derivatives

ZHANG Xin, LIU Shu-Xia, LI Shu-Jun, WANG Xue-Na, JIN Hai-Yan, CUI Jia-Li, LIU Yi-Wei, LIU Cheng-Zhan

2013, 34(9):  2046-2050.  doi:10.7503/cjcu20130386

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Two organic-inorganic hybrid compounds constructed from polyoxoniobates and transition metal coordination complexes, [Cu(TETA)]₄[VNb₁₂(VO)₄O₄₀][OH]·10H₂O(1) and [Cu(TETA)]₄\5[VNb₁₂(VO)₆O₄₀][OH]₅·5H₂O(2)(TETA=triethylenetetramine), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction analyses, IR spectra, X-ray photoelectron spectrum(XPS), powder X-ray diffraction(PXRD), thermogravimetric analysis(TGA) and elemental analyses. Compound 1 is a 3D tetra-capped vanadoniobates and compound 2 is a 3D hexa-capped vanadoniobates which are constructed from heteropolyoxometalates and [Cu(TETA)]²⁺ fragments. The result of bond valence sum calculations indicates that the vanadium centers of VO₄ tetrahedral in｛VNb₁₂｝Keggin unit in compounds 1 and 2 are in oxidation state +Ⅴ whereas the remaining vanadium centers are in oxidation state +Ⅳ. This is in line with the analysis of X-ray photoelectron spectrum.



Synthesis and Electrochemical Properties of Tetra (p-formylester-ferrocene-3-ethoxyphenyl) phenylporphyrin

WANG Ying, ZHANG Jia-Yan, ZHENG Zhi-Feng, ZHUANG Chang-Fu, LEI Fu-Hou

2013, 34(9):  2051-2056.  doi:10.7503/cjcu20130360

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Porphyrins have received the considerable attention because of their electron-transfer processes, photo-physics, biological processes and catalytic behaviors. This rapid development derives from their strong delocalization of π electron and conjugated macrocycles. The control of orientation of porphyrin chromophores can play a very important role. The functions of materials are related to the molecular alignments as well as the molecular structures. There were a number of reports on tetraphenylporphyrin derivatives, but those bearing the meso-substituted p-formyl-ferrocene group have been studied very little. In this paper, a symmetrical porphyrin with p-formyl-ferrocene group tetra(p-formylester-ferrocene-3-ethoxyphenyl)phenylporphyrin, was designed and synthesized through tetra(4-hydroxy-3-ethoxyphenal) porphyrin and formyl-ferrocene in CH₂Cl₂. The structure of tetra(p-formylester-ferrocene-3-ethoxyphenyl) phenylporphyrin was confirmed by UV-Vis, IR and ¹H NMR spectra. The UV-Vis absorption and fluorescence spectra indicated weak electronic interaction in ground state and strong electronic interaction in excited state between the ferrocene donors and the porphyrin acceptors. The cyclic voltammetry indicated that ferrocene substituents have a significant effect on the redox potentials.



Hydrothermal Preparation and Performance of CeO₂-TiO₂ Micro- and Nano-composites Deposited on Copper Mesh Film

DAI Chun-Ai, GAO Chang-Rui, FENG Lin

2013, 34(9):  2057-2062.  doi:10.7503/cjcu20130327

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CeO₂-TiO₂ micro- and nano-composites deposited on copper mesh film[(CeO₂-TiO₂)/Cu] were prepared with tetrabutyl titanate and cerium nitrate as raw materials, trisodium phosphate as mineralizer via one step facile hydrothermal method. The prepared materials were characterized by scanning electron microscopy(SEM), X-ray diffraction(XRD) and UV-Vis diffusion reflection spectrometry. The water wettabi-lity was tested using contact angle meter. Visual-light-activation of (CeO₂-TiO₂)/Cu was investigated by degrading methylene blue(MB, 20 μmol/L) under visible light irradiation. The results suggested that anatase TiO₂ dioxide and cerianite CeO₂ were prepared; compared with TiO₂, CeO₂ was easier to deposit on copper mesh film; the morphologies and structures of (CeO₂-TiO₂)/Cu were significantly affected by Ce(NO₃)₃·6H₂O content, Na₃PO₄ concentration, reaction time and reaction temperature. (CeO₂-TiO₂)/Cu displayed superhydrophilic property and visual-light photocatalytic performance.



Magnetocaloric Effect of La_0.62Ca_0.29K_0.09MnO₃ Epitaxial Film Prepared by Pulsed Laser Deposition

WU Xiao-Feng, HUANG Ke-Ke, HOU Chang-Min, GE Lei, CHU Xue-Feng, WANG Shan, FENG Shou-Hua

2013, 34(9):  2063-2067.  doi:10.7503/cjcu20130241

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La_0.62Ca_0.29K_0.09MnO₃(LCKMO) film was epitaxially grown on the (001) SrTiO₃(STO) single crystal substrate by pulsed laser deposition and a smooth and dense film was obtained by controlling the substrate temperature. The structure was characterized by 2D X-ray area detector and high resolution transmission electron microscopy, and the results indicate a high quality oriented growth of the film with the relationship of {001}LCKMO||{001}STO. At the magnetic field of 5 T, the maximum magnetic entropy change and relative cooling power of the film is 3.45 J/(kg·K) and 379.5 J/kg, respectively. A notable case is that the full width at half maximum of |ΔS_M| is 110 K, which is desirable for the Ericsson cycle, the excellent magneto caloric effect of the LCKMO film reveals its great applicative potentialities as magnetic cooling refrigerant.



Preparation and Performance of Ag/AgNO₃ Modified Titanate Nanotubes Films

PAN Yan, GUAN Shuang, GUO Yu-Peng, LIU Zhi-Hui

2013, 34(9):  2068-2076.  doi:10.7503/cjcu20130216

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Ag/AgNO₃ modified titanate nanotubes films were prepared by hydrothermal method and followed by photo-reduction method. The morphology, structure and composition of the product were characterized. The film exhibited high photocatalytic actibity and photochromic property. Ag/AgNO₃ acted as the active center and generated·O^-₂, HO₂· and ·OH. These strong oxidative free radicals not only degraded the organic matter, but also eliminated bacterium. Ag/AgNO₃ modified titanate nanotubes films would be a promising material in various of application areas in virtue of its excellent photocatalytic activity, photochromic property and antibacterial activity.



Characterization of Graphene Oxide Reduced by n-Butylmagnesium Chloride

HU Jiang-Pu, HUANG Ying-Juan, DONG Jin-Yong, WANG Yue-Xin

2013, 34(9):  2077-2083.  doi:10.7503/cjcu20130140

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Graphene oxide reduced by n-butylmagnesium chloride(n-BuMgCl) has been characterized systematically by elemental analysis, Fourier transform infrared spectroscopy(FTIR), X-ray photoelectron spectroscopy(XPS), Raman spectroscopy, X-ray diffraction(XRD), solid-state¹³C nuclear magnetic resonance(¹³C NMR), thermal gravimetric analysis(TGA), electrical conductivity measurement and atomic force microscopy(AFM). The results indicate that n-BuMgCl has a good efficiency in the reduction of graphene oxide. With the increase of n-BuMgCl concentration, the C/O molar ratio of the reduced graphene oxide(rGO) increased, and the interlayer distance of the rGO sheets decreased. The thermal stability of rGO has been improved significantly and the electrical conductivity of rGO increased to 3.6×10² S/m. AFM images show that the thickness of rGO sheets is larger than that of GO due to aggregation.



Analytical Chemistry

Metabolic Fingerprint and Effects of Aconite Alkaloid Components on the Activities of CYP450 Isozymes in Rat Liver Microsomes

BI Yun-Feng, LIU Shu, LI Xue, LIU Zhi-Qiang, SONG Feng-Rui

2013, 34(9):  2084-2089.  doi:10.7503/cjcu20130492

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The effects of the components of monoester and diester diterpenoid alkaloids(MDAs, DDAs) on the activities of hepatic microsomal CYP450 isozymes(CYP1A2, CYP2C, CYP2E1, CYP2D, CYP3A) were studied by ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS) combined with cocktail probe substrate' s method. The metabolic fingerprints of MDAs and DDAs' components were studied in rat liver microsomes using UPLC-Q-TOF/MS/MS. The results showed that the components of MDAs had strong inhibitory effects on the activities of CYP2C and 2D, the IC₅₀ value was 7.44 and 6.74 μmol/L, respectively. The components of DDAs had weaker inhibitory effects on the activities of CYP1A2, 3A, 2C and 2D, the IC₅₀ value was 39.48, 70.44, 17.36 and 86.04 μmol/L, respectively. Six metabolites of DDAs in rat liver microsomes were identified using UPLC-Q-TOF-MS/MS. They can be used as marked peaks for metabolic fingerprint of aconite alkaloids components.



Detection of H₂O₂ at Composite Membrane of [bmim] FeCl₄ and PVA Loading HRP Modified Graphene/nano Au

QU Jian-Ying, KANG Shi-Ping, LOU Tong-Fang, DU Xue-Ping

2013, 34(9):  2097-2101.  doi:10.7503/cjcu20121075

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Polyvinyl alcohol-ionic liquids(PVA-ILs) composite sol, graphenes(GS) and nano-Au were used to immobilize horseradish peroxidase(HRP). A novel hydrogen peroxide biosensor(HRP/PVA-ILs/HRP/nano Au-GS/GC) was obtained by immobilizing HRP with composite membrane of PVA-ILs on a glassy carbon(GC) electrode, which was modified with graphenes and nano Au. The experimental condition was optimized and the electrochemistry behavior of the HRP/PVA-ILs/HRP/nano Au-GS/GC biosensor in 0.1 mol/L HAc-NaAc+0.1 mol/L KCl(pH=6.5) including H₂O₂ was discussed. The response of the sensor to H₂O₂ is linear in the range of 9.55×10^-6—6.01×10^-3 mol/L with a correlation coefficient of 0.9990. The detection limit is 3.3×10^-7 mol/L. The experiments show that the biosensor exhibits high sensitivity, good reproducibility and stability and longer service life.



Organic Chemistry

Design, Synthesis and Activity Evaluation of Novel Bivalent HIV-1 Fusion Inhibitor

LING Yan-Bo, WANG Kun, JIANG Xi-Feng, CAI Li-Feng, LIU Ke-Liang

2013, 34(9):  2102-2107.  doi:10.7503/cjcu20130391

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Multivalent inhibitor is an efficient strategy for inhibitor design based on an additive effect of ΔG. In this work, we chose C34 and T20 as the template sequences to study bivalent inhibitors targeting HIV-1 gp41 NHR domain. We optimized the crosslink sites and linkers to improve anti-HIV activities of the bivalent fusion inhibitors. Compared to monovalent molecules, significant cooperative effects in the anti-cell-cell fusion activity were observed in the bivalent inhibitors, at either N- or C-terminal crosslink of both C34 and T20. β-Alanine may be the most suitable linker for N-terminal crosslink, while C34C is the best C-terminal crosslinked molecule. Specially, the anti-HIV IC₅₀ value of peptide BiCβAC34 was improved from 43.7 nmol/L to 6.4 nmol/L, indicating the two C-peptide chains had a cooperative effect. The results show that bivalent fusion inhibitor for gp41 design could appear a cooperative effect.



Synthesis and Ion Recognition Behavior of Benzo-18-crown-6 Modified Perylene Bisimide

WANG Li-Hua, JIANG Shan, ZHANG Zhi-Jun, ZHANG Heng-Yi, LIU Yu

2013, 34(9):  2108-2113.  doi:10.7503/cjcu20130350

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As n-type semiconductor, perylene bisimide and its derivatives have been widely used as liquid crystals, organogels, photoinduced electron transfer systems and organic electronic devices. The construction of supramolecualr assemblies based on the π-π stacking behavior of perylene bisimide has also attracted great interest. As a good acceptor for metal ions, 18-crown-6 has been used in various sensors. To combine the stacking and optoelectronic properties of perylene bisimide with the binding ability of crown ether and obtain a unique sensing behavior, a benzo-18-crown-6 modified perylene bisimide(1) was synthesized. The selectively binding behavior of host 1 toward metal cations and anions were investigated, respectively, using UV-Vis, fluorescence and EPR. Host 1 was found to show a selectively response toward Ba²⁺, which can affect the stacking behavior. Furthermore, host 1 exhibited a selectively response toward F^-, which should be attributed to the anion-π interaction between F^- and the perylene bisimide unit.



Synthesis and Interaction of L-dopa-L-Tyr-L-Tyr with DNA

ZHAO Dong-Xin, SUN Jing, ZHU Qi-Cong, LU Kui

2013, 34(9):  2114-2119.  doi:10.7503/cjcu20130072

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In order to improve the bioavailability of levodopa drug, reduing DNA damage, L-dopa-L-Tyr-L-Tyr was synthesized by Fmoc solid-phase synthesis, which was separated and purified by reversed-phase HPLC, and the product was characterized via ESI-MS,¹H NMR and ¹³C NMR. The interactions of L-dopa and L-dopa-L-Tyr-L-Tyr with ctDNA were investigated by ultraviolet, fluorescence spectra and agarose gel electrophoresis. The results showed that remarkable hypochromic effect was observed on the ultraviolet absorption spectra and the fluorescence quenching mechanism was static quenching by Stern-Volmer equation. The migration rate of pUC18 DNA became slow on the agarose gel electrophoresis, in the presence of increasing amounts of L-dopa and L-dopa-L-Tyr-L-Tyr. L-dopa and L-dopa-L-Tyr-L-Tyr might interact with DNA by intercalation binding. Compared with L-dopa, the interaction between L-dopa-L-Tyr-L-Tyr and DNA was stronger.



Synthseis and Antibacterial Activities of Some 3-(2-Hydroxy-4, 6-dimethoxyphenyl)-5-aryl-isoxazolines

JIANG Yu-Liang, HAN Qiao-Rong, ZHOU Wen-Long, XU Zhu-Xiong, WANG Bing-Xiang

2013, 34(9):  2120-2124.  doi:10.7503/cjcu20121141

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In the present paper, seven 3-(2-hydroxy-4,6-dimethoxyphenyl)-5-aryl-isoxazolines(2a—2g) were synthesized via the reaction of chalcone derivatives with hydroxylamine. All the synthesized compounds(2a—2g) were characterized by IR,¹H NMR, MS and elemental analysis. The study on the antibacterial activity of these compounds against Escherichia coli, Staphylococcus aureus, Bacillus subtilis and Pseudomonas aeruginosa indicated that compounds 2d and 2e had a certain inhibitory effect on all select strains while compound 2e showed good antimicrobial properties on E. coli and S. aureus.



Interaction of Amphotericin B/Sphingomyelin Monolayers at the Air/Water Interface

QIAO Jin-Jing, SUN Run-Guang, HAO Chang-Chun, YANG Jing, MA Xiu-Zi, WANG Xiao-Mei

2013, 34(9):  2125-2130.  doi:10.7503/cjcu20121137

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In this work, we chose sphingomyelin(SM) as the basic components of the monolayer, which is widespreaded in mammalian cells and takes an important role in biochemical reactions. Different proportion of amphotericin B/sphingomyelin monolayer's surface pressure and mean molecular area(π-A) curve was investigated by the Langmuir-Blodgett(LB) films technology, thermodynamic characteristics were also analyzed based on the π-A curve and the morphological changes of the surface were observed by atomic force microscopy(AFM). The results showed that the compressibility, stability and thermodynamic characteristics of AmB/SM monolayer depended on the mole faction of AmB and the surface pressure obviously. This may be related to the inhibition of Amphotericin B.



Design, Synthesis and Biological Activities of a Series of Piperazine Pyrimidine as CCR4 Antagonists

GONG Hong-Wei, QI Hui, SUN Wei, JIANG Dan, XIAO Jun-Hai, YANG Xiao-Hong, WANG Ying, LI Song

2013, 34(9):  2131-2138.  doi:10.7503/cjcu20120607

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CC chemokine receptor 4(CCR4) is a pivotal factor in the development of allergic inflammations, such as asthma, dermatitis and rhinitis. CCR4 antagonists have a huge potential in the therapeutics of the allergic diseases, and BMS-397 is the most potent CCR4 antagonists in the reported compounds. The structure-activity relationship of BMS-397 was studied and the large influence of the groups of pyridine and piperidine on the activity led us to modify these two sites. A series of piperazine pyrimidine derivatives was designed and synthesized. Their structures were characterized by ¹H NMR,¹³C NMR, MS and elemental analysis. The activities of all the newly synthesized compounds were evaluated using a chemotaxis inhibition assay. The results of biological activity experiment show that compound 8a was more potent than BMS-397. In the murine rhinitis model, budesonide was used as the calibration or comparison standard to assess the relative efficacy of compound 8a. The results show that compound 8a was more effective than budesonide, revealed excellent affinity to N-terminal of CCR4, and the apparent binding constant of CZE experiment result was (3.6179±0.5976)×10⁴ L/mol.



Synthesis and Evaluation of Cy7-Rituximab Targeting CD20 Antigen for in vivo Animal Fluorescence Imaging

LIN Xin-Feng, ZHU Hua, HONG Ye, YANG Zhi

2013, 34(9):  2139-2145.  doi:10.7503/cjcu20130368

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A new fluorescence molecular imaging probe Cy7-Rituximab was synthesized through the connection of fluorescence Cy7 dye and protein Rituximab. The probe was fully characterized by fluorescence spectrophotometer, SDS-PAGE and confocal microscopy. The uptake of Cy7-Rituximab probe in DLBCL cells was observed by laser scanning confocal microscope. Cy7-Rituximab probe of 0.4 mL(0.6 mg/mL) was injected to BALB/C nude mice through tail vein. The biodistribution of the novel probe Cy7-Rituximab was eventually observed, especially its specific concentration in spleen.



New Derivative of Tellurium Containing Cyclodextrin(6-AnSeCD) with Glutathione Peroxidase(GPx) Activity

LV Bing-Cong, DONG Seng, XUE Qiao, ZONG Hui, LV Shao-Wu, LUO Gui-Min

2013, 34(9):  2146-2151.  doi:10.7503/cjcu20121130

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Because the natural glutathione peroxidase(GPx) has some shortcomings such as instability, antigenicity and poor availability, scientists have paid much attention to its artificial imitation. In the present study, 6A,6A'-dianilino-6B,6B'-ditelluro-bis-β-cyclodextrin(6-AnTeCD) was designed and synthesized to imitate the antioxidant enzyme glutathione peroxidase(GPx). In this novel GPx model, tellurium replaced selenium as active atom, aniline group was incorporated into cyclodextrin in proximity to catalytic tellurium for increasing the stability of nucleophilic intermediate tellurolate, and β-cyclodextrin(β-CD) provided a hydrophobic environment for binding substrate in its cavity. The GPx activities and the kinetics of the mimics were assessed in classical coupled reductase assay. The antioxidant effect of the 6-AnTeCD was evaluated based on MTT assay. The results showed that 6-AnTeCD exhibits better GPx activity than those of 6-AnSeCD, 6-TeCD and Ebselen in the reduction of H₂O₂ by glutathione(GSH). As native GPx, a ping-pong mechanism was observed in steady-state kinetics studies. Moreover, the novel GPx mimic occupied merits of small molecular weight and low toxicity. Especially, the 6-AnTeCD was found that it could protect cardiac muscle cells from the injury induced by H₂O₂. These data demonstrated that and 6-AnTeCD has excellent potential in treatment of H₂O₂-mediated diseases.



Physical Chemistry

Theoretical Study on Second-order Nonlinear Optical Response of Lithiation Boron Nitride Nanotube

ZHOU Zhong-Jun, LI Xiao-Ping, HUANG Xu-Ri, WU Zhi-Jian, LI Zhi-Ru

2013, 34(9):  2152-2157.  doi:10.7503/cjcu20130378

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The development and application of second-order nonlinear optics(NLO) materials are always blocked by the nonlinearity-transparency trade-off. Improving this problem has become one of the most important researches in this field. In this paper, based on boron nitrogen nanotubes(BNNTs), the structures and nonlinear optical properties of lithiation boron nitrogen nanotubes Li_n-(n,0,l)BNNTs(n=6 and 8, l=2-4) were studied in theory. The results show that there are strong charge transfers occurring from Li atoms to boron nitrogen nanotubes, and the natural bond orbital(NBO) charges of Li atoms in Li_n-(n,0,l)BNNTs are 0.769—0.827 e, which is very close to +1, indicating that the multilithium salts of Li_n-(n,0,l)BNNTs are formed. And we found that with the increasing of the length and the width of tubes, first hyperpolarizabilities regularly increase. What is more important is that the UV-Vis adsorptions for Li_n-(n,0,l)BNNTs are mainly near 270—290 nm. When increasing the length of tubes, Li_n-(n,0,l)BNNTs have a small blue-shift, improving the nonlinearity-transparency trade-off. Besides, Li_n-(n,0,l)BNNTs also have large vertical ionization potentials(VIPs=5.85—6.00 eV), exhibiting higher stabilities. And thus Li_n-(n,0,l)BNNTs may be pro-mising candidate for high-performance nonlinear optical materials.



Statistical and Thermodynamic Properties of Star-branched Polymers Made by A_f+AB Type Polycondensation

TIAN Yue-Lan, BA Xin-Wu

2013, 34(9):  2158-2163.  doi:10.7503/cjcu20130377

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The thermodynamic properties of the star-branched polymers made by A_f+AB type polycondensa-tion were investigated by the principle of statistical mechanics. Starting with the canonical partition functions constructed from two viewpoints, the equilibrium free energy, the law of mass action and the size distribution of polymers were obtained. Furthermore, the specific heat and equation of state due to polymerization were given. In order to study the dimension of polymers in the system, the influences of the solvent quality on the average dimension of the star-branched polymers were discussed. The results showed the relationship between the average properties and thermodynamic and dynamic conditions, and thereby provided helpful clues on regulating relevant properties of the star-branched polymers.



Stability and Release Properties of Drug-loaded Pickering Emulsions by the Modified Sodium Alginate Activated SiO₂ Nanoparticles

YAN Hui-Qiong, LI Jia-Cheng, FENG Yu-Hong, HU Wen-Tao, LIU Ruo-Lin, LIN Qiang

2013, 34(9):  2164-2170.  doi:10.7503/cjcu20130299

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Pickering emulsions(W/O) loaded cyhalothrins were prepared by SiO₂ nanoparticles whose surface were activated using amphiphilic alginate derivative hydrophobically modified by cholesterol under the conditions of high speed stirring. And they were characterized by means of Fourier transform infrared spectroscopy(FTIR),¹H nuclear magnetic resonance(¹H NMR), fluorescence spectrum, dynamic light scattering, optical microscope and release studies. Experimental results showed that cholesterol groups had successfully grafted to the alginate molecular chains. The critical aggregation concentration of modified alginate was reduced from 1.26 mg/L to 0.28 mg/L, which showed good amphipathy. Alginate derivative(CSAD) and surfactant CTAB could be also adsorbed on the surface of SiO₂ nanoparticles with the corresponding zeta potential which were 16.4 and -30.7 mV, respectively. And the particle sizes were 583.3 and 438.4 nm, respectively. The release rate of the Pickering emulsions prepared by the SiO₂ particles activated by CSAD was more slowly. That may be the cross-linking action of CSAD which made the activated SiO₂ particles adsorbed on the oil-water interface form the relatively stable network structures or the interface membranes.



Catalytic Performance of the Ni/ZrO₂ Catalysts Prepared with the Hydrogel Method in Methanation of CO₂

LIU Quan, REN Jun, QIN Zhi-Feng, MIAO Mao-Qian, LI Zhong

2013, 34(9):  2171-2177.  doi:10.7503/cjcu20130285

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A series of Ni/ZrO₂ catalysts was prepared by the hydrogel method and characterized by X-ray diffraction(XRD), Brunauer-Emmett-Tetter(BET), transmission electron microscopy(TEM) and H₂ temperature programmed reduction(H₂-TPR), and their catalytic activities for the methanation of carbon dioxide were investigated. The results show that ZrO₂ presents an amorphous structure in the Ni/ZrO₂ catalysts after calcination at 450℃. During the H₂ reduction at the temperature of 400 ℃, the amorphous ZrO₂ carrier was partly transformed into tetragonal phase and Ni species were re-dispersed on the surface of ZrO₂. The metal-support interaction restrains the growth of NiO and ZrO₂, and electron cavity on amorphous ZrO₂ carrier favors the dispersion of Ni species. The NiO species interacted with amorphous ZrO₂ and tetragonal ZrO₂ has a definitive effect on the catalytic performance of the Ni/ZrO₂ catalysts. The highest catalytic activity was obtained on the Ni/ZrO₂ catalyst with a Ni/Zr molar ration of 0.707. Under the reaction condition, V(CO₂)/V(H₂)=1/4, gaseous hourly space velocity(GHSV)=1×10⁴ h^-1, P=0.5 MPa, 27% CO₂ conversion was obtained at a low temperature of 200 ℃. The conversion of CO₂ reached above 99% with the selectivity of CH₄ above 92% when the reaction temperature was improved to 280—320 ℃.



Investigation on the Aqueous-phase Hydrogenation of Bio-oil for Saturated Alcohols Production over Ni-B Amorphous Catalysts

YU Yu-Xiao, ZHANG Xing-Hua, WANG Tie-Jun, XU Ying, MA Long-Long, ZHANG Qi, ZHANG Li-Min

2013, 34(9):  2178-2183.  doi:10.7503/cjcu20130258

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Ni-B amorphous catalysts were prepared by chemical reduction of nickel chloride with potassium borohydride aqueous solution and characterized by X-ray diffraction(XRD), Brunauer-Emmett-Tetter(BET), scanning electron microscopy(SEM), transmission electron microscopy(TEM), inductively coupled plasma(ICP) techniques. The catalytic performances of model compounds and bio-oil to produce saturated alcohols were evaluated in a semi-batch reactor. The results showed that the conversion of model compounds(acetone, furfural and phenol) and the selectivity of saturated alcohols reached 99.99% and 90.00% at 110 ℃, 4.0 MPa(initial pressure). Under the conditions of 150 ℃ and 4.0 MPa, the yield of saturated alcohols reached 47.54%. High temperature of above 150 ℃ resulted in the transformation of amorphous phase to form crystal, which was attributed to the low catalytic activity. This work provides a new alternative for the production of saturated alcohols from bio-oil.



Theoretical Studies on Structures and Nonlinear Optical Properties of Superalkali Compounds Al₇X^0/-(X=F, Cl, Br, I)

XIAO Wen-Min, MA Na-Na, MA Teng-Ying, ZHANG Ting, YAN Li-Kai, SU Zhong-Min

2013, 34(9):  2184-2190.  doi:10.7503/cjcu20130250

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The structures and nonlinear optical(NLO) properties of a series of superalkali compounds, Al₇X^0/-(X=F, Cl, Br, I) were investigated by the means of density functional theory(DFT) calculations. The results indicate that the halogens have little influence on the geometry of the compounds. The present results indicate that Al₇X and Al₇X^- can be considered as superalkali duo to that the calculated vertical ionization energies(VIEs) are all lower than the ionization potential of Cs atom(IP=3.90 eV). In addition, three functionals(CAM-B3LYP, M06-2X and PBE0) were employed to calculate the NLO properties of these species. The results show that these compounds own large first hyperpolarizabilities(β₀), with the largest β₀ values of 21679 a. u. for Al₇I^-, which is 1.9 times of that of BLi₆F(11459 a. u.). Furthermore, it is worth noting that the values of β₀ are increased with the decrease of the electronegativity of the halogens for this type of compounds(Al₇F^0/- 7Cl^0/-7Br^0/-7I^0/-), which exhibit the same variations as the vertical ionization energies.



Super-hydrophobic and Super-oleophilic Properties of Taro Leaves and Their Application

LIU Bing, XU Wan-Fei, LI Hong, LIU Liu, SHEN Yu-Hua, XIE An-Jian

2013, 34(9):  2191-2195.  doi:10.7503/cjcu20130220

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The super-hydrophobic and super-oleophilic properties of taro leaves and their application were reported. The reasons that taro leaves possess super-hydrophobic and super-oleophilic properties were analyzed by static contact angle(CA) and scanning electron microscopy(SEM). The saturated oil absorption rate, sustained release and centrifugal oil retention of taro leaves dried at different temperatures were measured and analyzed by weighing method, sustained release property and centrifugation etc. The results show that the reverse side of the taro leaf is super-hydrophobic and its static water contact angle can reach 157.1° which is much larger than that of the front one(109.1°), and the sliding angles are not larger than 3°. It is also observed that the change of saturated oil absorption rate for the taro leaves shows certain regularity, and the highest saturated oil absorption(8.1 g/g) was obtained while the taro leaves dried at 200 ℃. Taro leaves own different capacity on fixing various oil spill. It can be known from results that taro leaves have strong capacity on fixing low volatile oil material and high centrifugal oil retention at high rotate speed.



Effect of Coating Layer Thickness on the Electron Injection Efficiency and Electron Lifetime in Dye-sensitized Solar Cells

HU Lin-Hua, MO Li-E, LI Wen-Xin, DING Yong, DAI Song-Yuan

2013, 34(9):  2196-2201.  doi:10.7503/cjcu20130071

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Sm₂O₃ was coated into the TiO₂ films by a dipping method, and Sm₂O₃ with thickness no more than 2 nm was obtained. The effects of thickness of Sm₂O₃ coating layer on the electron injection process and the electron recombination of dye-sensitized solar cells(DSC) were investigated. The results indicate that the electron injection efficiency decreases obviously in the thicker Sm₂O₃ coating films, while electrons have longer lifetime in the thicker coating film. As a result, the thicker coating thickness is, the lower conversion efficiency of DSC is. And the present research works indicate that the coating thickness of Sm₂O₃ layer within 0.4 nm is suitable for dye-sensitized solar cells.



Preparation and Photocatalytic Activities with Different Modes of Three-dimensionally Ordered Macroporous Composite Ag/TiO₂

LU Lu, LI Li, HUANG Xian-Dan, LI Zhao, ZHANG Xiu-Li, WANG Li-Li

2013, 34(9):  2202-2209.  doi:10.7503/cjcu20121175

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Using polystyrene(PS) latex sphere and triblock copolymer surfactant EO₂₀PO₇₀EO₂₀(P123) as templates, three-dimensionally ordered macroporous(3DOM) composite Ag/TiO₂ was prepared by the sol-gel method and calcination. The phase compositions, structures and morphologies of 3DOM Ag/TiO₂ were well-characterized by Fourier transform infrared(FTIR) spectra, X-ray diffraction(XRD), UV-Vis diffuse reflectance spectra(UV-Vis/DRS), X-ray photoelectron spectra(XPS), N₂ adsorption-desorption tests and scanning electron microscopy assisted X-ray energy dispersive spectroscopy(SEM-EDS). The results show that the pore structure of Ag/TiO₂ composite is distributed neat and orderly, whose wall is mesoporous, moreover, the composite belongs to three-dimensional ordered macroporous material. The 3DOM Ag/TiO₂ has anatase crystalline structure, in which Ag is metallic Ag⁰. Compared with Degussa P25, the absorption band of 3DOM Ag/TiO₂ is red-shifted ca. 30 nm to the visible region. For photocatalytic degradation of organic pollutants with different modes, including UV, visible light and mircomave-assisted irradiation, 3DOM Ag/TiO₂ shows better activities than Degussa P25 and Ag/TiO₂. In addition, 3DOM Ag/TiO₂ exhibits superior photocatalytic activity in the degradation process of different type organic pollutans.



Direct Electro-oxidation of Toluene Derivations on Graphite Electrode

ZHU Ying-Hong, LU Zai-Xiang, CHEN Qiong, MA Chun-An

2013, 34(9):  2210-2215.  doi:10.7503/cjcu20121107

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Direct electro-oxidation behaviors of toluene derivations(p-methoxy methylbenzene, p-xylene, p-chloro methylbenzene, p-tert-butyl methylbenzene) were studied by cyclic voltammetry(CV), in situ Fourier transform infrared spectroscopy(in situ FTIR), and constant potential electrolysis on graphite electrode in sulfuric acid and acetone solutions. The direct electro-oxidation behaviors of the four toluene derivations were similar. The negative-going band at 1710 cm^-1 is the stretching vibration peak of carboxyl group of aromatic aldehydes, and the positive-going band at 1130 cm^-1 shows the consumption peak of methyl of toluene derivations. The main electro-oxidation products are aromatic aldehydes detected by gas chromatography-mass spectrometry(GC-MS). The yield of p-methoxy benzaldehyde could reach up to 70.9% in the sulfuric acid system at 40 ℃.



Polymer Chemistry

Preparation and Properties of Halogen-free Fire Retardant Acrylonitrile Copolymer

REN Yuan-Lin, XIN Peng-Yue, SU Qian, CHENG Bo-Wen

2013, 34(9):  2216-2222.  doi:10.7503/cjcu20130458

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Acrylonitrile(AN)-vinyl acetate(VAc) copolymer [P(AN-co-VAc)] was synthesized via aqueous phase precipitated radical copolymerization of AN and VAc using K₂S₂O₈-NaHSO₃ as initiator. The VAc unit of P(AN-co-VAc) was selectively hydrolyzed with KOH aqueous under different pH values. The halogen-free fire retardant AN copolymer was prepared by the phosphorylation reaction among phosphoric acid, urea and the hydrolyzed P(AN-co-VAc). The structure of AN copolymer was characterized by nuclear magnetic resonance hydrogen spectrum(¹H NMR), Fourier transform infrared spectroscope(FTIR), and the thermal property of them was studied by differential scanning calorimetry(DSC) and thermogravimetric analysis(TGA). The number-average molecular weight(M_n) and polydisperisity index(PDI) of the obtained P(AN-co-VAc) were determined by gel permeation chromatography(GPC). The char residue of the halogen-free fire retardant AN copolymer was analyzed by FTIR and SEM. The results show that AN is really copolymerized with VAc and P(AN-co-VAc) can be synthesized successfully. VAc unit is quickly hydrolyzed with the increase of pH. DSC indicates that with the increase of mass fraction of VAc in P(AN-co-VAc), the temperature of cyclic exothermic peak(T_p) improves, and T_p reaches to 328 ℃ with the mass fraction of VAc being 25%, while T_p of fire retardant AN copolymer can be 340 ℃. TGA demonstrates that the char residue of fire retardant AN copolymer at 800 ℃ is 55%, which is higher than that of P(AN-co-VAc) being 41%, it fully proves that fire retardant AN copolymer has good char forming capability. The fire retardant mechanism of fire retardant AN copolymer belongs to condensed phase flame retardant mechanism.



Z-Average Radius of Gyration of Polymers in the Ternary Self-Condensing Vinyl Polymerization System with Unequal Reactivity

HONG Xiao-Zhong, GU Fang, WANG Hai-Jun, BA Xin-Wu

2013, 34(9):  2223-2227.  doi:10.7503/cjcu20130422

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The Z-average radius of gyration of hyperbranched polymers formed in the ternary self-condensing vinyl polymerization system was studied by the method of Monte Carlo simulation, in which the unequal reactivity was taken into account. As a result, the effects of the reactivity difference in two types of active centers, the molar ratio of inimers to monomers, the molar ratio and functionality of core initiators were discussed. It is found that these factors can give rise to a significant influence on the Z-average radii of gyration of hyperbranched polymers with and without the core initiator. This provides some useful clues for regulating the dimension and structure of the hyperbranched polymers in the relevant experiments.



Rheological Behavior of Carbon Black Filled Polystyrene Melts

CHEN Meng-Ting, TAN Ye-Qiang, SONG Yi-Hu

2013, 34(9):  2228-2232.  doi:10.7503/cjcu20130293

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Steady and dynamic rheological behavior of carbon black(CB) filled polystyrene(PS) composites were investigated. The CB/PS composites exhibit percolation transition at critical CB volume fraction(φ) of 0.06. The nonlinear rheology from dynamic strain sweep was related to the breakdown of particle-particle and particle-polymer interactions at small strains and the disentanglements of macromolecular chains at large strains. Analyzing the linear dynamic rheology of the composites according to the two-phase model revealed that the strain amplification factor A_f(φ), characteristic moduli and relaxation factor of the filler phase varied as a function of temperature. Dependence of A_f(φ) on φ followed the Guth equation and the diffusion-controlled cluster-cluster aggregation model. The shape factor and fractal dimension of the "filler phase" decreased with increasing temperature, suggesting that, as temperature was increased, the diffusion-controlled CB particle aggregation process was accelerated and the strain amplification effect was weakened. The elastic and viscostic characteristic modulus components of the "filler phase" exhibited scaling dependences on φ. At φ>0.06, both characteristic moduli of the "filler phase" and their scaling exponents demonstrated decrease tendencies with increasing temperature and the variation of the elastic component was slightly higher than the viscostic component revealing different temperature dependences of the elastic and viscostic characteristic modulus components of the "filler phase".



Synthesis and Properties of Poly(indenofluorene-triphenylamine) for Organic Field Effect Transistors

ZHANG Wei-Min, FENG Yu, DIAO Kai-Sheng, SUN Li, HONG Fang, SU Zhi-Xing, HU Yu-Ping

2013, 34(9):  2233-2238.  doi:10.7503/cjcu20130139

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Novel materials for organic field effect transistor——poly(indenofluorene-triphenylamine)(pIFTPA1—4) were synthesized and characterized by NMR and gel permeation chromatography(GPC). The organic field effect transistors(OFETs) based on these polymers were investigated. It was observed that stable amorphous thin films were formed in the devices, with better charge-carrier mobility than poly(triphenyl-amine)(pTPA). In four polymers synthesized, pIFTPA4 presents the highest hole mobility, as high as 4×10^-2 cm²/(V·s), with an ON/OFF ratio in excess of 10⁶.