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    10 November 2011, Volume 32 Issue 11
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    Contents
    Cover and Content of Chemical Journal of Chinese Universities Vol.32 No.11(2011)
    2011, 32(11):  0. 
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    Letters
    Synthesis and Crosslinking of Macrocyclic Aryl Ether-ketone Terminated Polyimide
    ZHANG Li-Mei, YUE Xi-Gui*, JIANG Zhen-Hua
    2011, 32(11):  2465-2467. 
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    A novel macrocycle-terminated polyimide oligomer and the model compound, which were considered as the most simple molecule to be representative of the oligomer, were prepared. The aromatic ether ketone macrocycle was prepared by aromatic nucleophilic substitution from (3-methoxy)phenylhydroquinone and difluorine compound under pseudohigh-dilution condition. The polyimide oligomer exhibited high thermal stability due to its wholly aromatic structure. Under heating treatment, the oligomer and the model compound can form fully aromatic thermoset polyimide by ring-opening reaction without catalyst. After crosslinking, the polyimide showed much higher glass transition temperature and excellent thermal stability with temperature at 5% mass loss above 550 ℃.
    Articles
    Luminescence of IRMOF3-sal Controled by Metal Ions
    WANG Shu-Hua*, ZHANG Jin-Mei, CHEN Chao, ZHENG Teng-Fei, FANG Xiu-Zhong
    2011, 32(11):  2468-2472. 
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    A series of IRMOF3-Msal(M=Mg, Zn, Co, Cd, Ni, Eu, Nd, Pr and Tb) was prepared via capturing the metal ions by IRMOF3-sal prepared by postsynthetic modification(PSM) of the isoreticular metal-organic framework(IRMOF-3). We hope it can provide a new approach for the design and preparation of fluorescent porous metal organic frameworks(MOFs). An isoreticular metal-organic framework(IRMOF-3) modified with salicylaldehyde(sal) by postsynthetic modification(PSM) capturing metal ions to yield IRMOF3-Msal(M=Mg, Zn, Co, Cd, Ni, Eu, Nd, Pr, Tb). Their structures were characterized by IR spectra, elemental analysis and  powder X-ray diffraction(XRD). The measurement and analysis of fluorescence spectra indicate that the emission peak of IRMOF3-Msal is blue-shift and IRMOF3-Mgsal displays the strongest relative fluorescence intensity.
    Handedness Inversion in Preparing Helical 1,2-Ethylene-silica Nanotubes
    HOU Feng-Wen, WANG Hai-Rui, WANG Li-Wen, LI Bao-Zong, LI Yi*, YANG Yong-Gang
    2011, 32(11):  2473-2477. 
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    A chiral anionic amphiphilic compound derived from D-valine was synthesized. The self-assembly behavior of this compound in solution and in gel was studied using circular dichroism. Helical 1,2-ethylene-silica nanotubes were obtained through a sol-gel transcription method using the assembly of this chiral compound as template and a co-structure-directing agent, 3-aminopropyltrimethoxysilane. It was found that the handedness of 1,2-ethylene-silica nanotubes can be controlled by tuning the concentration and pH value of the reaction mixture. However, the reaction temperature and water/ethanol volume ratio in the reaction mixture did not affect the handedness of the nanotubes.
    Preparation of Chain-like  CaCO3 Nanoparticles with Hydrophobic Properties via Double  Carbonation Route
    GUAN Shuang, AN Dong-Min, ZHENG Yun-Hui, GAO Xiao-Yan, MA Yue-Jia, WANG Zi-Chen*
    2011, 32(11):  2478-2482. 
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    Double carbonation route for the synthesis of hydrophobic chain-like nanometer calcium carbonate was studied. In the process, citric acid and cetyl acid were used as an organic substrate to induce the nucleation and modify the surface of calcium carbonate separately. The operating parameters such as temperature and the concentration of the organic substrate were varied to study their influences on the active ratio and contact angle of calcium carbonate particles. The products were characterized by transmission electron microscope(TEM), X-ray powder diffraction(XRD), Fourier transform infra-red(FTIR) and thermo gravimetric analysis(TGA).The results show that hydrophobic chain-like nanometer CaCO3 crystals can be obtained in the presence of citric acid and cetyl acid. Whereas, only cubic CaCO3 crystals can be obtained without citric acid and cetyl acid.
    One-step Hydrothermal Synthesis of TiO2 Nanowires and Their  Photocatalytic Activities
    WEI Qiu-Fang, CHEN Yong-Jun*
    2011, 32(11):  2483-2489. 
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    Titanium dioxide(TiO2) nanowires were synthesized by one\|step hydrothermal method   using tetrabutyl titanate, isopropanol and sodium hydroxide as starting materials. The synthesized TiO2 nanowires were characterized by scanning electron microscopy(SEM), X-ray diffraction(XRD) and energy dispersive X-ray spectrometry(EDX). The effects of reaction temperature, concentration of sodium hydroxide and reaction time on the formation of the nanowires were investigated. It is found that the optimum reaction temperature, concentration of sodium hydroxide and reaction time for the formation of high quality TiO2 nanowires are 180 ℃, 10 mol/L and 24 h, respectively. The nanowires were still anatase phase even if the calcination temperature increased to 950 ℃, indicating that the phase transition of TiO2  from anatase to rutile was delayed. In addition, the photocatalytic activities of pure TiO2 nanowires and TiO2 nanowires doped with Eu were studied under the irradiation of 300 W UV-lamp for 60 min, using methyl orange solution as the target degradation material. The results indicate that the degradation ratio of Eu-doped TiO2 nanowires is 1.5 times   that of pure TiO2 nanowires, and the optimum doping amount of Eu is 1.6%.
    Hydrothermal In-situ Synthesis and Enhanced Photocatalytic Properties of SrTiO3/TiO2 Composite Nanofibers
    LI Yue-Jun, CAO Tie-Ping, WANG Chang-Hua, SHAO Chang-Lu*
    2011, 32(11):  2490-2497. 
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    Heterostructured SrTiO3/TiO2 composite  nanofibers were fabricated by in situ hydrothermal method using TiO2 nanofibers as both template and reactant. The morphology and structure of SrTiO3/TiO2 composite nanofibers were characterized via X-ray diffraction(XRD), field emission scanning electron microscopy(FESEM), energy-dispersive spectrometry(EDS), high-resolution transmission electron microscopy(HRTEM) and X-ray photoelectron spectroscopy(XPS).The as-fabricated heterostructured composite included SrTiO3 nanocubes assembled uniformly on the surface of TiO2 nanofibers. Compared with the pure TiO2 nanofibers, SrTiO3/TiO2 nanofibers exhibited enhanced photocatalytic activity in the decomposition of Rhodamine B(RB) under ultraviolet light. This material also showed good catalytic stability and the decolorizing efficiency of RB solution remained above 97% after 5 times recycle, and was easily separated, removed from the system after reaction and reuse. Finally, the growth mechanism of SrTiO3/TiO2 heterojunction and  the mechanism for the enhancement of photocatalytic activity of heterostructured nanofibers were discussed.
    Infrared Emission Enhancement and Wavelength Widen of Composite Oxide Powders
    ZHANG Kong, LIU Qing-Feng, LIU Qian*
    2011, 32(11):  2498-2503. 
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    A new kind of nanoscaled composite oxide powders was prepared by a sol-gel combustion method to study the effect of doping on the infrared radiation. When calcined at 1100~1200 ℃, anatase, zircon and cordierite phases were crystallized in the resultant composite powders, proved from XRD patterns. The microstructural features and infrared emission performance were observed and measured by TEM and IR spectrometer. The infrared emission performance of the powder-packed disk samples showed a higher emissivity in a wide infrared range of 1~22 μm. The infrared emission peak appeared at about 10 μm with a maximal value of 98%. With the doping of Ni2+ and Fe2+, the infrared emission intensity increased obviously, due to the enhancement of anharmonic interaction, causing lattice deformation of the substituted cordierite structure.
    Rapid and Sensitive Fluorescence Enhancement Method by Barbituric Acid Derivatives for the Determination of Melamine in Milk
    HUANG Hui, XIANG Dong-Shan, LI Li, LI Hai-Gang, ZENG Guo-Ping, HE Zhi-Ke*
    2011, 32(11):  2504-2508. 
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    A rapid and sensitive fluorescence enhancement method was developed for the determination of melamine in milk. In phosphate buffer solution(pH=7.0), the hydrogen bond between melamine(M) and 5-(9-anthracenylmethylene) barbituric acid(DBA) can be formed and the fluorescence intensity of melamine increased greatly when DBA presented. Under the optimized conditions, the linear dynamic range, the detection limit and the relative standard deviation were 12.5~1250 μg/L, 7.5 μg/L and 2.06%, respectively. Combined with the solid phase extraction monolithic column to pretreat the samples, the average value of recovery rates was 96.62%. The proposed method has been successfully applied for the determination of melamine in milk.
    Study on specific recognition for PDGF based on the competitive reaction between Aptamer-DNA and Aptamer-protein
    ZHENG Jing*, QIN Jia-Hua, GONG Chen, HUANG Huan, HE Pin-Gang, FANG Yu-Zhi
    2011, 32(11):  2509-2514. 
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    A specific detection approach for platelet-derived growth factor(PDGF) via the competitive reaction between Aptamer-DNA and Aptamer-protein was established. In the paper, SiO2-MB nanocomposite was synthesized by reverse microemulsion method. For this proposed aptasensor, aptamer was immobilized on the magnetic nanoparticles, and the complementary oligonucleotide was labeled with SiO2-MB nanocomposite, Through the hybridization between the aptamer and its complementary oligonucleotide, a certain amount of SiO2-MB nanocomposite was gathered onto the magnetic nanoparticles. In the presence of PDGF, the aptamer was in a conformational equilibrium between Aptamer-DNA and Aptamer-protein, the aptamer prefers to bind with PDGF, resulting in a significant decrease of the electrochemical signal of MB. Upon this, we were able to detect the binding events between the aptamer and the protein. The assay was highly sensitive for PDGF, and is interference from other proteins such as IgG, thrombin and lysozyme. The linear range of the PDGF is 5.51×10-17 ～1.01×10-15mol/L with a detection limit of 1.31×10-17mol/L.
    Novel Approach for Quality Evaluation of Traditional Chinese Medicine Based on Integrated Selected-ion Chromatograms
    ZHANG Yu-Feng, FAN Xiao-Hui, QU Hai-Bin*
    2011, 32(11):  2515-2520. 
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    A liquid chromatography-mass spectrometry(LC-MS) based fingerprinting method was developed to study the Shuangdan extracts prepared by Danshen and Danpi from different habits; the two-way LC-MS datasets were converted to one-way integrated selected-ion chromatograms(ISICs) by our homely-made software and their discriminate power together with total ion chromatograms(TICs) and retention time corrected TICs were evaluated by principle component analysis. The results showed that ISICs surpassed TICs and retention time corrected TICs to separate herbal extracts from different places of produce. This transformation approach is rather fast and compatible with large datasets. The ISICs having more chemical information than TICs could be directly exported to statistical softwares for further analysis, whose retention times do not need to be corrected.
    NMR-based Metabonomics Studies on Serum and Urine of Yang-deficiency Constitution
    LI Ying-Shuai, WANG Qi*, YUAN Zhuo-Jun
    2011, 32(11):  2521-2527. 
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    Nuclear magnetic resonance(NMR)-based metabonomics was applied to study the yang-deficiency constitution by analyzing metabolic profiling of serum and urine. The purpose of this study is to determine an array of characteristic metabolites in serum and urine samples from yang-deficiency constitution person and then to interpret these metabolites in possible metabolic pathway.  Serum and urine samples from 30 yang-deficiency constitution person with 30 balanced constitution person were collected. Differences in endogenous metabolites were detected on serum and urine samples from the yang-deficiency constitution group and control group using multivariate statistical analysis. Compared with the balanced constitution, the contents of lactate, very low density lipoprotein(VLDL)/low density lipoprotein(LDL), N-cetyl glycoprotein(NAc), fatty acid(FA), unsaturated fatty acid(UFA) are lower while the contents of glutamine, glucose, phosphatidylcholine(PtdCho), high density lipoprotein(HDL) are higher in serum of yang-deficiency constitution, and the content of creatinine is lower while the contents of lactate, DMA, citrate, hippurate are higher in urine of yang-deficiency constitution. The biomarkers supply new ways for the individual differences from the point of view of metabonomics. Yang-deficiency constitution has some metabolism disorder of energy, lipid and glucose, and also  has changes of organs functions.
    Preparation of Novel Molecular Imprinted Film/Au nanoparticlar Modified Electrode for Bromophos ethyl and Its Application
    WANG Jing-Jing, JIANG Xin, Lü Shi-Yan, WEI Guo-Fen, YE Tai, Lü Jian-Quan*
    2011, 32(11):  2528-2532. 
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    A novel molecular imprinted(MIP) film/Au nanoparticles(AuNP) modified glassy carbon electrode(GCE), L-Cys/AuNP/GCE(MIP), was prepared by electrochemical deposition of gold nanoparticles and electrochemical assembly of L-Cys at the surface of GCE using bromophos ethyl as template molecular. The results indicate that L-Cys/AuNP/GCE(MIP) can selectively recognize bromophos ethyl and be applied for the electrochemical determination of bromophos ethyl in the spiked sample. Under the optimized conditions, the electrochemical response is directly proportional to the bromophos ethyl concentration in the range from 2.5 to 17.5 μmol/L, with a detection limit(S/N=3) of 0.83 μmol/L. The experiment results also show that the L-Cys/AuNP/GCE(MIP) has good stability and reproducibility.
    Determination of Organophosphorus Pesticides Using a Biosensor Based on Acetylcholinesterase Immobilized by Au Nanoparticles/Sol-gel Composite Membrane
    SUN Chun-Yan*, LI Hong-Kun, PING Hong, WANG Er-Lei, ZHANG Min-Wei, LIU Jing-Bo*
    2011, 32(11):  2533-2538. 
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    Based on the inhibition effects of organophosphorus pesticides on acetylcholinesterase(AChE), an amperomerometric biosensor was developed by immobilizing AChE on glassy carbon electrode with the composite film of Au nanoparticals and chitosan-silica hybrid sol-gel. Using acetylthiocholine chloride as the substrate, the electrochemical determination method for organophosphorus pesticide was established with monocrotophos as a representative model for sensitivity tests. The experimental conditions were optimized according to the current response. The response of biosensor fabricated was related linearly to the concentration of monocrotophos in the range of 0.5~12.0 μg/mL with a detection limit of 0.02 μg/mL. The developed biosensor exhibited good reproducibility and acceptable stability, providing a simple method for the analysis of organophosphorus pesticide.
    Theoretical Study on the Tautomerization of Cartap Intermediate and Its Isomer
    YU Guan-Ping*, MA Yi, LIU Peng-Fei, YAN Tao, LI Zheng-Ming*
    2011, 32(11):  2539-2543. 
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    The byproduct 1-(dimethylamino)-2,3-dithiocyanatopropane(2) can be recycled and partly converted into its isomer 2-(dimethylamino)-1,3-dithiocyanatopropane(1), the key intermediate of Cartap, and finally achieved dynamic equilibrium, which can be used to increase the yield.  Effects of temperature, catalyst and solvent on the tautomerization of compound 1 and its isomer 2 were investigated. The rearrangement mechanism was studied by density functional theory(DFT) method at B3LYP/6-31G(d) level. The calculation results indicated that the ring closure leading to aziridinium ion and further ring opening by thiocyanate at less substituted aziridine carbon atom via an SN2 mechanism. The solvent effect(toluene, chloroform, acetone, methanol, ethanol, acetonitrile and DMSO) on tautomerization was also taken into account via polarizable continuum model(PCM).  Ionization of a neutral substrate results in charge separation, and solvent polarity has a greater effect at the transition state than that for the reactants. Polar solvents lower the energy of the transition more than the solvents of lower polarity. The results show that the solvent effect plays an important role which was supported by experiment data.
    Inclusion Interactions of Cucurbit[8]uril with Methotrexate
    MA Yan-Hui, HUANG Ying, ZHU Qian-Jiang*, ZHANG Jian-Xin, XUE Sai-Feng, TAO Zhu
    2011, 32(11):  2544-2547. 
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    Cucurbit[n]urils(Q[n]) which have the unique structure with hydrophobic central cavity and hydrophilic carbonyl group portals, are a class of molecular containers that bind to a variety of cationic and neutral species with high affinity and therefore show great promise as a drug delivery system.  In this paper, interactions of cucurbit[8]uril(Q[8]) with anti-cancer drug MTX in different proton forms were studied in details by UV absorption spectroscopy.  The result shows that the inclusion ratio of Q[8] and MTX+ is 1:1,  and the formation constant is (7.64±1.52)×104 L/mol.  Moreover, the thermodynamic parameters of the complex formation were also determined, and it shows that the formation of the inclusion complexes between MTX and Q[8] is entropy controlled, suggesting that hydrophobic forces are the main driving forces.  The inclusion complex was further proved by 1H NMR.
    Novel Method of Phosphatase Detection Based on Cationic Conjugated Polymer and Enzymatic Substrate Probe
    ZHANG Xiao-Ping, HUANG Yan-Qin*, FAN Chun-Hai, HUANG Wei*
    2011, 32(11):  2548-2553. 
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    A novel method was  developed for phosphatase detection based on  cationic conjugated polymer(CCP) and enzymatic substrate.  The CCP associated with the fluorescein-labeled anionic adenosine triphosphate(ATP) by electrostatic attractions and fluorescence resonance energy transfer(FRET) from the CCP to the fluorescein-labeled ATP occurred.  When phosphatase was added, it catalyzed the hydrolysis of phosphate groups from its substrate, ATP, and the final product adenosine was neutral, which made the CCP detached from adenosine.  Then the FRET efficiency decreased.  The results show that the degree of FRET efficiency decrease is related to the concentration of phosphatase.  This detection method has the advantages including easy operations, real-time response, and high sensitivity.  It can also sensitively assay other enzymes that promote the changes of the charge density of substrates; moreover, it provides a promising application in drug screening based on the inhibition of enzymatic activity.
    Isolation and Identification of Novel Flavonoids from the Bract of Zea mays L
    ZHANG Mu-Xin, LIU Yin-Yan, SUN Wei, YANG Xiao-Hong, WANG Guang-Shu*
    2011, 32(11):  2554-2557. 
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    Zea mays(maize), a member of the Poaceae, is the most economically important crop in China, about 24 million hectares of Zea mays has been cultivated each year in China, there is about 600 kg of the bract of Zea mays per hectare, and thus the resources of the bract of Zea mays is extremely rich.  Although there are some pharmacological activity researches about  radical scavenging activity against hydroxyl radical and superoxide anion radical, reducing blood lipid and inhibiting arteriosclerosis, the studies on phytochemical constituents of the bract of Zea mays have not  been reported. In order to utilize the resources of the bract of Zea mays, we investigated the chemical constituents of the bract of Zea mays. The air-dried bract of Zea mays was extracted with 95% ethanol at room temperature, the extract was subjected to Diaion AB-8 column chromatography eluated with ethanol-H2O, and the eluate was further chromatographed on silica gel and Sephadex LH-20 columns repeatedly to yield 4 flavonoid compounds. Their structures were identified as tricin(1), tricin 5-O-β-D-glucopyranoside(2), tricin 7-O-β-D-glucopyranoside(3), tricin 7-O-[β-D-apifuranosyl(1→2)]-β-D-glucopyranoside(4) by spectral analysis(UV, IR, MS and 1D, 2D NMR), respectively. Among them, compound 4 is a new flavonoid compound, compounds 1, 2 and 3 are firstly isolated from this plant.
    Synthesis of N,N'-Dimethyl-1,3-benzenediamine by Reduction Method with NaBH4 and I2
    MAO Pei-Qing, LIU Li-Fen*, XU De-Zhi, LI Yi-Ming, GAO Cong-Jie
    2011, 32(11):  2558-2561. 
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    The common aromatic polyamide composite reverse osmosis(RO) membrane is easy to be oxidated. N,N'-Dimethyl-1,3-benzenediamine(DMMPD)as a key functional monomer can be used to prepare the chlorine resistance RO membrane by interfacial polymerization technology.  In this work, the DMMPD was synthesized by reduction method with composite reductant NaBH4-I2. The m-phenylenediamine as substrate was first reacted with the acylating agent of formic acid to get the intermediate N,N'-diformyl-m-phenylenediamine, then the resulting intermediate was reduced by NaBH4-I2 to obtain the final product DMMPD, the synthetic technology was further optimized through orthogonal test, and the proposed mechanism of reduction was discussed. The chemical structures of all products were identified via infrared spectra(IR), hydrogen nuclear magnetic resonance(1H  NMR) and mass spectragraph(MS). This current method for preparing the DMMPD has several advantages, including accessible substrate, mild reaction condition, relatively low cost and high yield.
    Synthesis and Optical Property of Bis{[5,5'-10,20-bis(phenyl)-15(4-pyridyl)porphyrin]Zinc(Ⅱ)} Butadiyne
    Lü Feng, CHEN Guo-Hui, LIU Tian-Jun*
    2011, 32(11):  2562-2567. 
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    Near-infrared fluorescence technology has been applied in biomarkers, bioanalysis, cell imaging and bio-tissue imaging in vivo. Especially the fact that organisms have low scattering effect and background interference in near-infrared region, increases near-infrared image sensitivity and penetrating depth in biological tissue.  Near-infrared fluorescence agents are promising reagent for detection and imaging in deep tissues and organs. Porphyrins have extension electronic conjugated structure, good optical stability, acceptable fluorescent quantum yields, and good biocompatibility, which endow porphyrins with near-infrared emission have more advantages than other dyes in fluorescence imaging. In this paper, bis{[5,5'-10,20-bis(phenyl)-15(4-pyridyl)porphyrin]zinc(Ⅱ)} butadiyne was designed and synthesized as near-infrared fluorescent compound. The structures of the compounds were confirmed by means of 1H NMR and MS. UV-Vis spectra were measured by spectral method and fluorescence imaging was recorded by HWHR optical instrument.  Deep fluorescence imaging in vitro was studied with biotissue as model. The results show that bis{[5,5'-10,20-bis(phenyl)-15(4-pyridyl)porphyrin]zinc(Ⅱ)} butadiyne has strong fluorescence in near-infrared region. Fluorescence imaging of biotissue in vitro can achieve structural information in a depth more than 1 cm.  So this butadiyne linked prohyrin dimmer partially meets the demand of near-infrared imaging and can be potentially applied in the fluorescence imaging diagnosis in vivo in future.
    Absolute Configuration Determination for Natural Products(Ⅰ)——Absolute Configuration Determination for Ketone, Lactone and Alcohol by Comparing Computed Optical Rotations and  13C NMR with the Experimental Results
    SHEN Lan, ZHAO Sheng-Ding, ZHU Hua-Jie*
    2011, 32(11):  2568-2573. 
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    Optical rotation and 13C NMR computations for five natural products, vidalenolone(1), 2-(3-dihydroxy-3-methylbutyl)benzene-1,4-diol(2), 5,6,7,7a(S)-tetrahydro-2-hydroxy-1-(p-hydroxyphenyl)-3H-pyrolizin-3-one(3), 3,4-dihydro-4,8-dihydroxy-6-methoxy-7-methyl-1(2H-|naphthalenone(4) and 6-(R)-(4'-oxopentyl)-5,6-dihydro-2H-pyran-2-one(5), were performed at the B3LYP/aug-cc-pVDZ//B3LYP/6-31G(d) levels for assigning their absolute configurations. The computational results matched the experimental results well. One compound's 13C NMR chemical shifts were corrected based on the computational 13C NMR results and earliest reports.
    Preparation and Characterization of a Novel Embolic Nano-in-Micro Drug Delivery System
    LIU Yuan-Gang, MAO Hong-Hao, WANG Shi-Bin*, SUN Xue-Zhan
    2011, 32(11):  2574-2580. 
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    A  novel poly-L-arginine/chitosan/calcium alginate nano-in-micro(NiM) drug delivery system was prepared using emulsification combined with electrospraying method. Fluorescent labelling test proved that the nano-in-micro structure of NiM was successfully constructed. Bovine serum albumin(BSA) and 5-FU were used as model drugs and the release profiles of NiM as carriers to a single drug and two different drugs were investigated respectively. The results show that the cumulative release rates are 16.3%(5-FU) and 4.9%(BSA) in 0.5 h, and 82.6%(5-FU) and 10.9%(BSA) after 132 h. Zero-order kinetics, first-order kinetics, Ritger-Peppas model and Higuchi model were used to study the release dynamics of these swelling drug delivery systems and Ritger-Peppas model was proved to be the best one which could fit the experimental data effectively.  It is concluded that the new NiM system can avoid burst release, slow down the release rate and achieve sequential release of different drugs, and it is expected to have potential applications in drug delivery system.
    Effects of  Annealing on the Surface Photoelectronic Properties of TiO2 Nanotube/Nanowire Composite Arrays
    YANG Feng, CAI Fang-Gong, KE Chuan, ZHAO Yong*, CHENG Cui-Hua
    2011, 32(11):  2581-2585. 
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    TiO2 nanotube/nanowire composite arrays were fabricated on the Ti substrate via anodic oxidation method. Annealing effects on the surface photoelectronic properties of TiO2 nanotube/nanowire composite arrays were studied by surface photovoltage spectrum(SPS) and the electrical field induced surface photovoltage spectrum(FISPS). The results show   that the bound excitons exist at the edge of conduction band both in as-prepared and annealed TiO2 nanotube/nanowire composite arrays. The build-in field in as-prepared TiO2 nanotube/nanowire composite arrays is weak and the bound excitons can inverse antisymmetrically under external field. After being annealed, TiO2 nanotube/nanowire composite arrays were crystallized from amorphous structure, the build-in field is increased, but the SPS responses related to the bound excitons could exhibit only under positive field.
    Theoretical Investigation of the Reaction Mechanism of Cypridina Luciferin Analogues
    SUN Ying, REN Ai-Min*, LI Zuo-Sheng, MIN Chun-Gang, REN Xue-Feng, FENG Ji-Kang
    2011, 32(11):  2586-2592. 
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    In order to study the chemiluminescent reaction mechanism of Cypridina luciferin, a series of 6-aryl-2-methyllimidazo[1,2-a]pyrazin-3-(7H)-ketone rings based derivetives(named MIPa—MIPd) was chosen as studied objectives in this work. We employed the DFT//B3LYP/6-31G* method to calculate the activation energy and the fluorescence lifetime(τ) of the products in the reaction from the dioxetanones to amidopyrazines in the gas phase, dimethyl sulfoxide(DMSO), and diglyme(DG). The calculated results indicate that Cypridina luciferin analogues possessing the electron-donating aryl group have lower activation energy(ΔEa) and the solvent has significant effect on activation energy(ΔEa), which is lowest in DMSO. The fluorescence-quantum-yield of path Ⅱ is higher in DMSO than that in path Ⅰ, but it reverses in DG.
    Molecular Dynamics Simulation on the Inter-diffusion of Supercritical Lennard-Jones(L-J) Mixture
    GE Song, CHEN Min*
    2011, 32(11):  2593-2597. 
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    Molecular dynamics simulation has been carried out to study the self-diffusion in pure supercritical fluid and Maxwell-Stefan mutual diffusion in binary supercritical Ar-Kr solution. In the supercritical fluid, the temperature dependence of the self-diffusion coefficient obeys the Arrhenius relation quite well, and the calculated activation energy decreases with increasing density. In the binary supercritical Ar-Kr solution, the concentration dependences of both self-diffusion and Maxwell-Stefan mutual diffusion coefficients are obtained. The self-diffusion coefficients of Ar and Kr increase with increasing molar fraction of Ar. The calculated Maxwell-Stefan diffusion coefficients are larger than those predicted by the Darken relation. The results also show that the velocity cross correlation is not negligible and positive, this system can not be treated as an ideal system which is different from Ar-Kr solution in the normal state where the Darken relation is applicable.
    Stabilizing Effect of Lamellar Liquid Crystal Gels on Microfoams
    YAN Yong-Li*, DENG Qiang, MENG Mei
    2011, 32(11):  2598-2604. 
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    Highly stable microbubble dispersions with mean bubble diameter of less than 100 μm were prepared simply by nonionic surfactant of glyceryl monostearate(GMS). The microstructure, phase transition and rheological properties on these colloidal systems were studied using optical microscopy, freeze fracture transmission electron microscopy(FF-TEM), differential scanning calorimetry(DSC) and a controlled stress rheometer in an attempt to explore its stabilization mechanisms. The experimental results reveal that the GMS molecules are adsorbed at the air/water interface, which results in the self-aggregate of lamellar liquid crystal gel phase. The rigid lamellar could arrest the Laplace-pressure-driven dissolution due to the ordered and tightly stacking of GMS molecules. The interfacial crystallization as well as the formation of a three-dimensional network of GMS in the continuous phase determines the stability against coalescence behavior of the microbubbles. The stable microbubbles could sustain for more than 10 months without occurrence of phase separation and collapse. It is concluded that the stability of the microfoams prepared solely by GMS surfactant is attributed to the presence of lamellar liquid crystalline gels covered at the gas/liquid interface. The role of liquid crystal gel in stabilizing microfoams can be related to its effect on several mechanisms including hydrodynamic drainage, mechanical strength of the liquid film and the diffusion rate of entrapped gas.
    Synthesis of Chiral Salen Mn(Ⅲ) Immobilized on Novel Layered Crysalline Hybrid Support Zinc Poly(styrene-phenylvinylphosphonate)-phosphate as Effective Catalysts and Asymmetric Epoxidation of Unfuntionalized Olefins
    HU Xiao-Yan, FU Xiang-Kai*, LIU Zhi-Jian, XU Jiang-Wei, LUO Yun-Fei
    2011, 32(11):  2605-2612. 
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    A new type of organic polymer-inorganic hybrid material zinc poly(styrene-phenylvinylphosphonate)-phosphate was designed and synthesized under mild conditions. The characterized results show that the new hybrid material is crystalline with regular layered structure, and the ideal structure model is proposed. A series of new heterogeneous catalysts was obtained by grafting chemical modified on support and subsequently axial coordination with chiral salen Mn(Ⅲ) complexes. The supported catalysts were applied to the enantioselective epoxidation of unfunctionalized olefins with m-CPBA as oxidants. The heterogeneous catalysts exhibited higher activity and enantioselectivity than in homogeneous catalyst system, and excellent reusability. It was surprised that the heterogeneous catalysts afforded remarkable increases of conversion and e.e. values in the absence of co-catalyst 4-methylmorpholine N-oxide(NMO), which increases the possibility for industry applications.
    Density Functional Theory Studies on the Electronic Properties of Dilacunary γ-Keggin Polyoxometalate Anions
    ZHANG Di, DOU Zhuo, ZHANG Ting, YAN Li-Kai*, SU Zhong-Min*
    2011, 32(11):  2613-2617. 
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    The geometrical structures and electronic properties of dilacunary γ-Keggin polyanions [γ-Xn+W10O36](12-n)-(X=AlⅢ, SiⅣ, PⅤ, SⅥ, GaⅢ, GeⅣ, AsⅤ, SeⅥ) were investigated via density functional theory(DFT) methods. The results show that the bond lengths between central tetrahedral oxygen atom Oa and central heteroatom X, as well as tungsten atom depend on the central heteroatom X. However, the sizes of XO4 are independent with the central heteroatom. The highest occupied molecular orbital(HOMO) of [γ-Xn+W10O36](12-n)- mainly concentrates on the bridge oxygen atoms. Except for [γ-SeW10O36]6-, the lowest unoccupied molecular orbital(LUMO) of polyanion is from d orbitals of tungsten atoms. The energies of HOMO and LUMO of [γ-Xn+W10O36](12-n)- depend on the central heteroatom X. The LUMO energy decreases with the increasing of the atomic numbers, and the central atoms are in the same row in periodic table.
    Performance of Pt-Ru/C Catalysts Doped with W, Ni and Sn for Electrocatalytic Oxidation of Methanol in Alkaline Media
    DUAN Dong-Hong, ZHANG Zhong-Lin, ZHANG Tao, LIU Shi-Bin*, HAO Xiao-Gang, LI Yi-Bing
    2011, 32(11):  2618-2625. 
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    The catalysts of Pt-Ru-M/C(M=W, Ni, Sn) with different atom ratio were prepared by colloidal method. The surface composition and crystal structure of nano-particle supported by carbon black were characterized by X-ray diffraction and X-ray photoelectron spectroscopy. The catalyst activity in different methanol and NaOH concentration electrolytes was measured by cyclic voltammeter. The results show that the perfor-mance of methanol electro-oxidation on the Pt-Ru/C catalysts can be improved markedly by doping with Ni and W, and be reduced by doping with Sn, and the peak current density on Pt5-Ru4-Ni0.7/C reaches 835.2 mA/mg and the onset potential of methanol electro-oxidation is 0.11 V lower than that of Pt5-Ru5/C in 1.0 mol/L NaOH+1.0 mol/L CH3OH.
    Stability of Carbon Supported Pd/C Catalyst in Direct Formic Acid Fuel Cell
    SHEN Juan-Zhang, CHEN Ying, YANG Gai-Xiu, TANG Ya-Wen, LU Tian-Hong*
    2011, 32(11):  2626-2629. 
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    In order to understand the reason for the poor electrocatalytic stability of the Pd/C catalyst for formic acid oxidation, the changes in the structure and the electrocatalytic performance of the Pd/C catalyst after dipping in the formic acid solution for a certain time were investigated using X-ray diffraction spectroscopy and electrochemical methods. It is found that the relative crystallinity of the Pd particles of Pd/C catalyst increases from 1.73 to 3.34 and the average size decreases from 4.4 nm to 1.8 nm  after dipping in formic acid solution for 15 d. The electrocatalytic activity and stability of the Pd/C catalyst for formic acid oxidation decrease. The peak current density of formic acid oxidation decreases  from 9.3 mA/cm2 to 6.7 mA/cm2. It may be due to the certain dissolution of Pd in the Pd/C catalyst and the catalytic decomposition of formic acid at the Pd/C catalyst. This result may supply a new approach for exploring the reason for the poor electrocatalytic stability of the Pd/C catalyst for the formic acid oxidation.
    Optoelectronic Properties of ZnO-C60 and ZnO-MWCNT Composite Coating Electrodes Fabricated by  Electrophoretic Deposition
    HUANG Zi-Yang*, LIANG Guang-Chao, FAN Lou-Zhen
    2011, 32(11):  2630-2634. 
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    ZnO-C60 and ZnO-MWCNT composite coating electrodes were fabricated by electrophoretic deposition on indium tin oxide(ITO) conductive glass surface, and the strength between coating and conductive glass was enhanced by heating treatment sequentially. The surface photography of electrode coatings was characterized by scanning electron microscopy(SEM), the optoelectronic properties were measured by CHI 705 electrochemical analyzer and PMI\|E electrochemiluminescence system. The results show that the ZnO-C60 composite coating electrode possesses a high stability and a strong photo-generated current over 30% compared with base current(where Δi=0.022 μA), the latter was studied by amperometric curve(i-t) and open circuit potential time(OCPT) under visible light irradiation. The ZnO-MWCNT composite coating electrode ownes a high stability and a strong electrochemiluminescent capability, the latter was investigated by cyclic voltammetry(CV) and amperometric curve  of electrochemiluminescence system. These two composite coating electrodes are hopeful of developing a brand optoelectronic and electrochemiluminescent electronic devices.
    Metastable Zone Properties of H3BO3 in Different Concentrations of KCl and NH4Cl Solutions
    KONG Fan-Zhi, DONG Ya-Ping*, MENG Qing-Fen, PENG Jiao-Yu, LI Wu
    2011, 32(11):  2635-2639. 
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    The solubility and ultra solubility of boric acid in aqueous were measured in the presence of different concentrations of KCl and NH4Cl from 0 ℃ to 25 ℃. The metastable zones and the crystal nucleation orders of H3BO3 were calculated. Effects and action mechanism of KCl and NH4Cl on metastable zone property of H3BO3 were studied. The result shows that the existence of KCl makes the metastable zone of H3BO3 move to higher temperature by increasing solubility of H3BO3. According to the adsorption effect, NH4Cl makes metastable zone of H3BO3 move to lower temperature. Concentration variation of KCl and NH4Cl in evaporation of Nayishan oilfield brine is one of the reasons that boron crystallizes dispersedly.
    Effects of Substrates on Deposition of Zinc from Flowing Alkaline Zincate Solutions
    CHENG Jie, WEN Yue-Hua*, XU Yan, CAO Gao-Ping, YANG Yu-Sheng
    2011, 32(11):  2640-2644. 
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    The effects of substrates including nickel foil, nickel\|plated perforated steel strip, on deposition/dissolution behavior of zinc from flowing concentrated alkaline zincate solutions were investigated. The results show that almost no changes of concentration differences occur in flowing electrolytes, leading to no cathodic peaks appearing in cyclic voltammograms. At a scan rate above 10 mV/s, no variation of voltammograms for the zinc deposition/dissolution with scan rate is observed. This indicates that zinc deposition/dissolution peak currents are not only dependent on scan rate but also  related to the time of zinc deposition. The substrate, nickel-plated perforated steel strip, is characterized by high-H2-overpotential to excellent chemical stability. The mode of mass transportation is changed due to its special perforated structure. As a result, the polarization of zinc deposition is effectively reduced. Piled tightly zinc deposition is formed around the pores of the substrate. High zinc deposition efficiency is obtained with large current and capacity of zinc deposition. After 4 charge\|discharge cycles, the coulombic efficiency reaches over 95%. Therefore, the nickel\|plated perforated steel strip is a favorable substrate electrode suited for zinc deposition from flowing alkaline zincate solutions.
    Effect of LiNO3 as Additive on Electrochemical Properties of Lithium\|sulfur Batteries
    XIONG Shi-Zhao, XIE Kai*, HONG Xiao-Bin
    2011, 32(11):  2645-2649. 
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    The effect of LiNO3 as additive on electrochemical properties of lithium-sulfur batteries was investigated by charge-discharge and electrochemical impedance spectroscopy(EIS). The effect of LiNO3 on lithium anode was investigated by scanning electron microscope(SEM) and the interacting mechanisms of LiNO3 was discussed. It was found that LiNO3 adopted as additive of electrolyte formed protective surface film on lithium electrode. The film resulted in passivation at the surface of the electrode and prevented the parasitic reaction between higher-order polysulfide and lithium electrode. Cycle life and capacity of lithium-sulfur batteries were improved because the film prevented the formation of irreversible Li2S on lithium electrode. The initial discharge capacity of lithium sulfurbatteries with LiNO3 is 1172 mA·h/g. A reversible capacity of 629 mA·h/g  after 100 cycles was obtained.
    Electrochemical Preparation of Shape-controlled Pd Nanoparticles and Their Electrocatalytic Properties
    YAN Xiao-Hui, DIAO Peng*, XIANG Min
    2011, 32(11):  2650-2656. 
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    The electrochemical preparation of shape-controlled palladium nanoparticles(PdNPs) and their catalytic activity toward methanol electrooxidation were reported. PdNPs were prepared on indium tin oxides(ITO) conductive substrates by a two-step constant potential deposition method, in which Na2PdCl4 and citrate were used as precursor and capping agent. The morphology, size, and growing density of PdNPs can be controlled by varying the electrodeposition parameters, such as nanoseeds generation potential, particle growth potential, the concentration of citrate and bromide, and the deposition temperature. The Pd nanohorn arrays, spherical, flower-like and polyhedronal PdNPs were  prepared on ITO substrates. The electrocatalytic properties for methanol oxidation on PdNPs with different morphologies were investigated in alkaline solution. Compared with other PdNPs, the Pd nanohorns demonstrated a much larger surface area on an ITO substrate with a fixed area due to their larger height. As a result, the Pd nanohorn arrays exhibite a higher catalytic activity toward methanol electrooxidation, making them a potential candidate for alkaline direct fuel cell anode materials.
    Dissipative Particle Dynamics  Simulation and Experiments of Main Influence Factors of Conformation of Starch Emulsion
    ZHENG Lu-Si, XIE Xin-An*, DING Nian-Ping, LI Yan
    2011, 32(11):  2657-2662. 
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    With cyclohexane as oil phase, amylose as aqueous phase, meanwhile Span60 and Tween60 as emulsifiers influence factors of conformation of starch emulsion were investigated by dissipative particle dynamics(DPD) simulation. It is shown from DPD simulations that  the system becomes equilibrated after 6000-step simulation, the size of micro particle decreases firstly and then increases  with the increase of the content of emulsifiers, but increases with the increase of starch content and the decrease of the content of cyclohexane. The parameters of forming the stable starch emulsion system are 7＜oil-water ratio≤20 and  9%＜content of emulsifier≤18%. The results show that the sizes of the microspheres decrease with the increase of  the content of emulsifier(from 11% to 15%), but increase when  content of emulsifier  higher than 15%. The experimental results are consistent with the simulation results.
    In-situ Acetylation of Pine Wood Chip in 1-Allyl-3-methylimidazolium Chloride(AmimCl) Ionic Liquid
    CAO Yan, WANG Xue-Jing, LI Hui-Quan*
    2011, 32(11):  2663-2666. 
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    Pine wood chips were successfully acetylated in an ionic liquid 1-allyl-3-methylimidazolium chloride(AmimCl). Without any catalyst, acetylated pine with the weight percentage gain(WPG) in the range of -89% to 156% could be prepared in one\|step. Under the homogeneous state, the WPG of acetylated pine can be easily controlled by the acetylation time, temperature and molar ratio of Ac2O/OH. The obtained acetylated pine was characterized by means of FTIR, 13C NMR, TGA and SEM. The NMR and FTIR results show obvious peaks for the acetylation; the TGA result shows that the thermal stability of acetylated wood can reach as high as 205 ℃, which is a bit lower than the original pine; the SEM result shows that the acetylated pine has a dense and homogeneous structure. Therefore, this study presents a promising approach and green process for in-situ wood chip acetylation efficiently.
    Synthesis of Amphiphilic Block Codendrimers Gx-PBE-b-Gx-PMPA(OH)x2 and Study on Temperature Dependence of Multiple Hydrogen Bonds
    YUAN Fei, LI Qiu-Yue, WANG Wei*
    2011, 32(11):  2667-2673. 
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    Block codendrimers Gx-PBE-b-Gx-PMPA were synthesized through a coupling reaction between Gx-PBE dendrons and Gx-PMPA dendrons(x=1, 2, 3). Amphiphlic block codendrimers Gx-PBE-b-Gx-PMPA(OH)x2 were further prepared through removing acetonide protecting groups on the periphery of the Gx-PMPA blocks. Their chemical structures were characterized by 1H NMR and 13C NMR spectroscopies, MALDI-TOF(or FD) mass spectroscopy and FTIR spectroscopy. Meanwhile, FTIR spectrometer equipped with a heating stage was used to study the change of the hydrogen bonds in-between hydroxyl groups with increasing temperature. A widened transition region with increasing dendron generation was found. This result can indicate that with increasing dendron generation the ability of forming intermolecular hydrogen bonds decrease due to the three-dimensional structure of higher generation dendron.
    Crystallization Behavior of Modified Hydroxyapatite/Poly(L-lactide) Nanocomposites
    WEI Jun-Chao*, MA Li-Li, DAI Yan-Feng, CHEN Yi-Wang, ZHANG Pei-Biao, CUI Yi, CHEN Xue-Si*
    2011, 32(11):  2674-2679. 
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    Biocompatible poly(γ-benzyl-L-glutamate) modified hydroxyapatite/poly(L-lactide)(PLLA) nanocomosites were prepared via solvent-mixing method. Their melting and crystallization behavior were characterized by differential scanning calorimetry(DSC) and polarized optical microscopy(POM). The results show that the glass transition temperature of PLLA is 60.3 ℃ and that of the composite can reach 65.8 ℃. After isothermally crystallized at 140 ℃, the spherulites diameter of modified HA/PLLA composites was only 16.7%\_66.7% compared with that of PLLA and the melting point of the composite can rise to 184.4 ℃.
    Synthesis of (PAA-b-F127-b-PAA)-β-lactoglobulin Conjugate with Improved Emulsifying Properties
    MENG Ling-Min, LIANG Rong, SHI Ke, HUANG Qing-Rong, SHI Tong-Fei*
    2011, 32(11):  2680-2684. 
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    Poly(acrylic acid)-b-F127-b-poly(acrylic acid)(PAA-b-F127-b-PAA) was synthesized through atom transfer radical polymerization(ATRP) in combination with the subsequent hydrolysis of tert-butyl groups using excess trifluoroacetic acid(TFA). The (PAA-b-F127-b-PAA)-β-lactoglobulin conjugate was successfully synthesized using water soluble 1-ethyl-3-(3-dimethyllaminopropyl) carbodiimide hydrochloride(EDC?HCl), a carbodiimide derivative, as the conjugation agent. Fluorescence spectroscopy indicated that the ternary structure of protein was maintained even conjugation to PAA-b-F127-b-PAA. The conjugate exhibited significantly better emulsifying properties than that of pure β-lactoglubulin.
    Synthesis and Structure Characterization of 3,3'-Bisazidomethyloxetane-3-azidomethyl-3'-methyloxetane Random Copolymer
    ZHANG Chi, LI Jie, LUO Yun-Jun*, LI Xiao-Meng, GE Zhen
    2011, 32(11):  2685-2690. 
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    3,3'-Bisazidomethyloxetane-r-3-azidomethyl-3'-methyloxetane random copolymer[p(BAMO-r-AMMO)] was synthesized by cationic ring opening polymerization using 1,4-butanediol/BF3/Et2O initiator system. Polymerization mechanism of active chain end and activated monomer was discussed in the presence of Lewis acid. The effect of polymerization temperature on molecular weight and molecular weight distribution of product was analysed by GPC. The results indicate that molecular weight is controllable and molecular weight distribution is relatively narrow under 15 ℃. 1H NMR and 13C NMR were also used to character composition and micro-sequential structure of random copolymer. The results show that the composition of copolymer is 1:1, which is accordance with molar feed ratio of monomers; alternating degree is nearly 50%; average sequence length of chain segment is 2 for both BAMO and AMMO, so the two structural units are in random distribution.
    Adsorption of Bovine Serum Albumin on the Surface of Medical Polyurethane Elastomer
    YIN Hong-Gen, HOU Feng-Wen, LI Yi*, CHENG Rong-Shi
    2011, 32(11):  2691-2695. 
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    A special isophorone diisocyanate(IPDI) type polyurethane(PU) elastomer with good mechanical property was prepared. Heparin was grafted on the surface of this PU elastomer and a PU-Hep elastomer was obtained. The dynamic adsorption of bovine serum albumin(BSA) on PU elastomers was investigated by immersing the PU and PU-Hep elastomers in dilute BSA aqueous solution and measuring the viscosity change of the solution. The results show that BSA macromolecules quickly accumulate on the surface of PU and PU-Hep elastomers, however, it needs a long time to reach the adsorption equilibrium. The conformational chang of BSA macromolecules happens in bulk solution after adsorption on the PU and PU\|Hep elastomers.
    Synthesis and Properties of Electroactive Hyperbranched Polymer
    CHAO Dan-Ming, YAO Lei, CHEN Da-Peng, HE Li-Bing, JIA Xiao-Teng, LIU Hong-Tao, WANG Ce*
    2011, 32(11):  2696-2699. 
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    We prepared an electroactive hyperbranched polymer containing phenyl-capped aniline tetramer segment in the chains by integration of A2+B3 strategy with oxidative coupling polymerization. The structure of hyperbranched polymer was characterized by FTIR, 1H NMR spectra, and gel permeation chromatography(GPC). A reversible electrochemical property like common oligoanilines was found. The thermal properties and dielectric properties were also investigated. With an exciting structure, reversible electrochemical properties and dielectric properties, the electroactive hyperbranched polymer would be used as electromagnetic interference(EMI) shielding and microwave absorbing materials in the future.
    Synthesis of One-dimensional Polyaniline Nanostructures in the Presence of Cationic Surfactant
    YIN Hua-Jie, YANG Ji-Ping*
    2011, 32(11):  2700-2705. 
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    Branched polyaniline nanofibers with average diameter of 115 nm and curly polyaniline nanowires with average diameter of 75 nm were successfully synthesized in the presence of cetyltrimethylammonium bromide(CTAB), with HCl as the dopant acid and ammonium peroxydisulfate(APS) as oxidant. Their structure yields were 90% and nearly 100% and the conductivity were 1.6×10-2 S/cm and 9.3×10-2 S/cm, respectively. It was found that the polyaniline nanostructures were co-affected by both the concentration of HCl and the [An]/[CTAB] molar ratios. Furthermore, it could be concluded the induced\|effect of the floccules formed by CTAB and S2O2-8  was the key factor to the generation of polyaniline one-dimensional nanostructures based on the observations of the growth processes of polyaniline nanowires.
    Synthesis and Properties of Photoresponsive Polymer Materials Containing Fluoro-Azobenzene
    LI Xiang-Liang, TANG Qian, GUO Cong-Cong, MA Rong, CHANG Wen-Bin, GONG Cheng-Bin*
    2011, 32(11):  2706-2710. 
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    Decafluoroazobenzene was synthesized with satisfied yield via 1,2,3,4,5-pentafluoroaniline as the starting material and FeSO4?7H2O supported KMnO4 as the oxidant. Decafluoroazobenzene was hydrolyzed in t-BuOH in the presence of KOH, and then methacrylated with methacrylic chloride. Finally, a photoresponsive functional monomer, (4-methacryloyloxy)nonafluoroazobenzene(MANFAB), was obtained. The structure of MANFAB was confirmed by GC-MS, elemental analysis, and NMR. The photoresponsive properties of MANFAB were studied by UV-Vis. Photoresponsive cross-linked polymer containing fluoro-azobenzene were prepared by radical polymerization with trimethylolpropanetrimethylacrylate as the cross-linker, (4-methacryloyloxy)nonafluoroazobenzene as the functional monomer, and AIBN as the initiator. After polymerization, the photoisomerizations of fluoro-azobenzene chromophore were retained. And the photoresponsive properties of the polymer materials were also studied by UV-Vis spectra.
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