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    10 July 2008, Volume 29 Issue 7
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    高等学校化学学报2008年第29卷第7期目次
    2008, 29(7):  0.  doi:
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    下期目次预览
    2008, 29(7):  0.  doi:
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    综合评述

    Layer-by-Layer Assembled Microcapsules: Fabrication, Stimuli-responsivity, Loading and Release
    TONG Wei-Jun, GAO Chang-You*
    2008, 29(7):  1285-1298.  doi:
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    Layer-by-layer(LBL) assembly of polymers and polymers/small molecules on colloidal particles forms core-shell particles, which produce hollow microcapsules with a layered structure after core removal. This article reviews the recent progress in driving forces for fabricating the LBL microcapsules, intelligent stimuli-responsivity and loading and release properties. The manipulation of the electrostatic and hydrogen bonded microcapsules by chemical crosslinking in terms of their structures and properties is first presented. Then the microcapsules based on new driving forces, i.e. covalent interaction, base pair and host-guest interaction, are introduced. The microcapsules thus obtained are responsive to pH, temperature, charge, light, electricity, magnetic field and chemical compounds. The typical loading and release properties and techniques established so far, such as direct encapsulation by the multilayers, pre-adsorption or pre-incorporation into the templates and charge controlled deposition, are discussed subsequently. Finally, aiming at the target delivery of the microcapsules and functional capsule devices, the methods for arraying the microcapsules on the substrates based on the electrostatic interaction and bioconjugation are described.
    研究论文
    Synthesis, Characterization and the Third-order Nonlinear Optical Properties of a Derivative of {Mo102}-type Porous Inorganic Nano-fullerene
    ZHOU Yun-Shan1,2*, HAN Rui-Xue1, ZHANG Li-Juan1, LI Yu-Hao1, ZHANG Li-Hui1
    2008, 29(7):  1299-1303.  doi:
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    A small spherical inorganic fullerene nano-capsule anion of a formula [{(Mo)Mo5O21(H2O)4·SO4}12{MoⅤO(H2O)}30]12- bearing 20 {Mo6O6}-type rings/channels built up from 102 Mo atoms and O atoms were synthesized by reacting a highly charged spherical inorganic fullerene nano-capsule anion with the formula [{(MoⅥ)Mo5ⅥO21(H2O)6}12{Mo2ⅤO4(SO4)}30]72- bearing 20 {Mo9O9}-type rings/channels with guanidineacetic acid under acidic conditions at room temperature. The crystal structure of the resulted compound were characterized by X-ray single-crystal diffraction, elemental analysis, TG-DTA analysis and FTIR, UV-Vis, and ESR spectrascopies. It crystallizes in a triclinic system space group P1, a=2.5377(5) nm, b=2.5932(5) nm, c=3.9547(8) nm, α=83.58(3) °, β=86.15(3) °, γ=75.55(3) °, V=25.023(9) nm3. Meanwhile, its third-order nonlinear optical properties were studied using Z-scan technique with 5 ns laser pulse at λ=532 nm. The third-order nonlinear refractive index of the title compound is determined to be γ=-3.29×10-18 m2/W and the third-order nonlinear susceptibility χ(3)=-1.04×10-23 m2·V-2, showing strong nonlinear self-defocusing refractive effects.
    High-yield Synthesis of MCM-48 at Low Temperature
    QU Feng-Yu1*, LI Jian-Hua1, LIU Feng-Hua1, JI Ming-Yan1, ZHU Guang-Shan2*
    2008, 29(7):  1304-1306.  doi:
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    A low cost, fast, and feasible synthesis method of MCM-48 was proposed by adjusting the temperature(303—313 K) and co-surfactant. The product yield of the synthesized MCM-48 was up to 98%. Powder X-ray diffraction(XRD), transmission electron microscopic(TEM) images, scanning electron microscopic(SEM) Images, and nitrogen adsorption-desorption isotherms were used to characterize the synthesized samples.
    Synthesis, Optical and Thermal Properties of Novel Schiff Base Complexes Containing Porphyrin Copper(Ⅱ) and Zinc(Ⅱ)
    LUO Guo-Tian*, ZHENG Sheng-Wei, XU Qing-Bing
    2008, 29(7):  1307-1311.  doi:
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    5-(p-Benzylideneamino)phenyl-10, 15, 20-triphenylporphyrin copper(Ⅱ), zinc(Ⅱ) complexes and 5-[p-(4-nitrobenzylideneamino)]phenyl-10, 15, 20-triphenylporphyrin copper(Ⅱ), zinc(Ⅱ) complexes were designed and synthesized by the reaction of pyrrole and benzaldehyde et al.. The intermediates and target compounds were characterized by FTIR, FAB-MS, UV-Vis spectra and 1H NMR. Furthermore, one of the target compounds was confirmed by single crystal X-ray diffraction.In addition, we also studied the thermostability and luminescent effect of the target compounds.The experiment results show that the strongest luminescent wavelength is 600 nm, which locates in the visible light area. The compounds decompose at 70 ℃ in the air.
    Effect of Hole-doping on the Spectrum Properties of One-dimensional Spin Chain Material Li1-xCuVO4(x≤0.1)
    DU Fei, WANG Chun-Zhong, LI Xu, LI Ang, CHEN Gang*
    2008, 29(7):  1312-1316.  doi:
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    One-dimensional spin chain materials Li1-xCuVO4(x≤0.1) were synthesized by solid state reaction. The X-ray diffraction show that Li1-xCuVO4(x≤0.1) was crystallized in inverse spinel structure. Raman measurement displayed 15 vibration models. The loss of Li+ had no effect on the long-range and short-range structure based on the X-ray diffraction and Raman spectrum. The X-ray photoemission spectra revealed that the valence state of O ion and V ion remained unchanged in the hole-doped materials, corresponding to the -2 and +5, respectively. The peak position of Cu2p shifted to the high binding energy in the doped materials, indicating the appearance of holes on the Cu2+ and therefore an existence of Cu3+.
    Preparation of Langmuir-Blodgett Monolayer Film of FePt Nanoparticles on Different Substrates Using Cycling Compression Method
    XU Bin, WANG Ying*, ZHANG Ya-Fei
    2008, 29(7):  1317-1320.  doi:
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    Recently, a lot of methods were devised to prepare an ordered arrangement of nanomaterials, such as self-organization, electrophoretic deposition, and Langmuir-Blodgett(LB), etc. The LB technique was proven a powerful and simple method to prepare the high-density nanoparticle monolayer and multiplayer film with controllable layer numbers and thickness. In this article, we introduced an improved LB method to fabricate the FePt nanoparticle monolayer film. The LB monolayer of FePt nanoparticles was fabricated on different substrates using a cycling compression method. The monolayers have a smooth surface and a high-density structure on hydrophobic surface as shown by the TEM and AFM image. The results show that the uniformity and stability of the monolayer can largely improve by this method, and the surface morphology of monolayers was varied between the substrates.
    Transport and Absorption of Chiral Metal Complexes d-[Co(EDTA)]- and l-[Co(EDTA)]- Across Caco-2 Cell Monolayers
    MU Yong-Ping1, WU Gang1,4*, QIAO Xiu-Wen2, GAO Yu-Xi3, ZHOU Li-She1 , HE Yan-Ling4
    2008, 29(7):  1321-1324.  doi:
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    The trasport rate of chiral complexes d-[Co(EDTA)]- and l-[Co(EDTA)]- across Caco-2 cell monolayers were measured by the kinetics method. The studies discover that there is an obvious difference about the trasport rate of d-[Co(EDTA)]- and l-[Co(EDTA)]- when they get across Caco-2 cell monolayers because of the chiral difference of the metal complexes. The results show that there is a chiral selectivity when chiral metal complexes were transported and absorbed across Caco-2 cell monolayers and imply that intestine would selectively absorb drugs of chiral metal complexes. The trasport rate of d-[Co(EDTA)]- and l-[Co(EDTA)]- passing through Caco-2 cell monolayers depends on the grads of the complexes concentration, it is shown that their transport model is as simple diffuse when they were transported and absorbed through Caco-2 cell monolayers.
    Synthesis, Characterization and Formation Mechanism of Single-Crystal WO3 Nanosheets via an Intercalation-chemistry-based Route
    CHEN De-Liang1*, WANG Hai-Long1, ZHANG Rui1, GUAN Shao-Kang1, LU Hong-Xia1, XU Hong-Liang1, YANG Dao-Yuan1, SUGAHARA Yoshiyuki2, GAO Lian3
    2008, 29(7):  1325-1330.  doi:
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    In this work an intercalation-chemistry-based method to synthesize tungstate and tungsten oxide nanosheets was described. A layered bismuth tungstate(Bi2W2O9) was used as the W-containing starting material. After the bismuth oxide layers were leached by a chloride acid, a protonated form, H2W2O7·xH2O with sizes of 5—15 μm, was achieved. The intercalation reaction of n-octylamine with H2W2O7·xH2O in heptane and the subsequent dissolution-recrystallization process led to the formation of tungstate-based inorganic organic hybrid nanobelts. Orthorhombic WO3·H2O nanosheets were obtained by removing the organic species of the as-obtained hybrid nanobelts. After the dehydration of the as-obtained WO3·H2O nanosheets at 250—450 ℃, monoclinic WO3 nanosheets were achieved. The results of XRD, TEM and SEM indicate that the obtained WO3·H2O and WO3 were single-crystalline nanosheets with areas of (200—500) nm×(200—500) nm and thicknesses of 10—30 nm. The SAED patterns suggest that the WO3·H2O and WO3 nanosheets possessed a reduced directions of [010] and [001], respectively. N2 adsorption measurement results indicate that the specific surface areas of the as-obtained WO3·H2O and WO3 nanosheets were up to 250 and 180 m2/g, respectively. The formation mechanisms for hybrid nanobelts, WO3·H2O and WO3 nanosheets were discussed. The proposed novel route was efficient in producing two-dimensional WO3 nanosheets on a large scale.
    研究快报
    A Rapid and Green Method for Synthesis of Copper Hydroxyphosphate
    SHEN Qi-Hui, ZOU Yong-Cun,WAN Li-Feng, LIU Wen-Ting, WANG Run-Wei*, QIU Shi-Lun
    2008, 29(7):  1331-1333.  doi:
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    Copper hydroxyphosphate was rapidly synthesized by using a novel hydrothermal method, in which phosphoric acid and copper acetate hydrate are two mainly raw materials in the procedure of preparation without the presence of ethylenediamine. Compared with the conventional method, this new method cost less with less reaction time and without damage to environment. The resultant copper hydroxyphosphate samples were characterized by X-ray diffraction(XRD), single crystal X-ray diffraction and Leica optical microscopy. The as-synthesized samples show significant activities to the hydroxylation of phenol. The exposure of special crystal planes(011) and (101) can be used to explain the high hydroxylation activities of as-synthesized copper hydroxyphosphate at 80 ℃.
    研究论文
    Sdudy and Application of Mitoxantrone Sensor Based on Molecular Imprinting
    WU Wu-Ai, YIN Zhi-Fen, WEI Jing-Rui, GUO Man-Dong*
    2008, 29(7):  1334-1338.  doi:
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    Under the condition of weak acidity, a sensitive film was prepared through the electropolymerization of o-aminophenol on a glassy carbon electrode surface in the presence of mitoxantrone which was considered as the template. A mitoxantrone sensor based on molecular imprinting was obtained. The sensor exhibits a good selectivity and sensitivity to mitoxantrone. The determination limit of the mitoxantrone was 1.6×10-7 mol/L, and a linear relationship between the peak current and the mitoxantrone concentration was found in the range from 3.3×10-7 to 1.0×10-5 mol/L and from 1.0×10-5 to 5.0×10-5 mol/L. Also, the configuration and characteristics of the film were investigated in detail.
    Fluorescence Spectrometric Study on the Interaction Between Umbelliferone and Bovine Serum Albumin with the Use of MCR-ALS
    LIU Gen-Lan1, NI Yong-Nian1,2*
    2008, 29(7):  1339-1343.  doi:
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    Under the imitated physiological conditions(pH=7.4), the interaction between umbelliferone and bovine serum albumin(BSA) was investigated by the fluorescence spectroscopy and the multivariate curve resolution-alternating least squares method(MCR-ALS). In this work, the interaction between umbelliferone and bovine serum albumin(BSA) was studied by performing two different kinds of titration modes. The two spectroscopic data matrices were augmented, and then the information of experiment data was increased. The augmented experiment data matrix was analyzed by the MCR-ALS method. This procedure allowed the recovery of the concentration profiles for each species and the calculation of the [BSA]∶[Umbelliferone] ratio in the complex and the apparent equilibrium constant. The effect of umbelliferone on the conformation of BSA was also analyzed via synchronous fluorescence spectrometry.
    Preparation of Oligoguluronate Sulfates by Solid Phase Acid Degradation and Analysis by Negative-ion Electrospray Tandem Mass Spectrometry
    ZHAO Xia*, FU Hai-Ning, YU Guang-Li, WANG Jin-Xia, LI Xiao-Jun, GUAN Hua-Shi
    2008, 29(7):  1344-1348.  doi:
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    Polyguluronate sulfate(PGS) with a high degree of sulfate substitution was prepared by chemical sulfation with sulfur trioxide pyridine complex(SO3-Py) on the basis of polyguluronic acid(PG), which was isolated from the hydrolysate of alginate. The optimum sulfation conditions were determined by orthogonal design method and the structure of PGS was confirmed by 2D-NMR spectroscopy. A new environment-friendly degradation method(the so called solid phase acid degradation) was developed to prepare PGS oligosaccharides, in which 732# resin was used as an acidic degradation medium. The results of degradation show that the weight average relative molecular weight(Mw) of PGS oligosaccharides was lower than 3000, when the ratio of 732# resin is 200 mg/mL and mass fraction of PGS is 2%, degradation temperature is 100 ℃ and degradation time is 6 h. Thirteen PGS oligosaccharides(F1—F13) were obtained by Bio-Gel P6 column separation. The polymerization degree of F1—F13 is from one to thirteen, respectively, demonstrated by ESI-MS analysis. The solid phase acid degradation method was used to solve the problems of environmental pollution, inorganic salts separation and corrosion of reactors, which are universal in traditional acid degradation methods, and it provides a new approach to preparation of oligosaccharides.
    Cyp17a1 Gene Expression in Rat’s Adrenal and Prostate After Orchiectomy
    WANG Wan1,2, HE Yong-Xin2, CHEN Jun2, LI Xue2, LUO Guo-An1,2*, WANG Yi-Ming2
    2008, 29(7):  1349-1351.  doi:
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    In this paper the change law of Cyp17a1 gene expression in the process was studied, in which the rats’ adrenal secretes androgen after orchiectomy. The Cyp17a1 gene expression in adrenal and prostate tissues was detected via real-time fluorescent quantitative PCR on different time points, which were before orchiectomy and 1 week, 2 weeks, 3 weeks, 4 weeks after orchiectomy, respectively. The results indicate that Cyp17a1 gene expression in adrenal would increase after orchiectomy, and reach the maximum when 3 weeks after. That Cyp17a1 gene exists in rat’s prostate tissue was discovered for the first time. The conclusion is that adrenal have the function of compensation, increasing the secretion of androgen after orchiectomy. It is presumed that prostatecan synthesizes DHEA as well.
    Synthesis of Distyrylbenzene Based Two-photon Fluorescent Probe and Its Recognition of Metal Ions
    WANG Fu-Qiang, LI Ya-Ming*, YU Hai-Bo, LIU Jun, WANG Xiu-Na, JIN Kun, ZHANG Rong
    2008, 29(7):  1352-1355.  doi:
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    A novel two-photon fluorescent probe DMNS2O was synthesized and characterized via NMR and MS. It contains an 1-oxa-4,10-dithia-7-aza-cyclododecane receptor and a distyrylbenzene fluorophore. Crystal structure was detected through X-ray diffraction. Consequent analysis results show that both CC double bonds exist as trans configuration, and the dihedral angle between the three benzene ring were 24.6°and 37.5°, respectively. The maxima absorption and emission of DMNS2O in acetonitrile were at 460 nm and 600 nm, respectively. Variations of emission spectra were detected upon the addition of different metal ions. It was found that the addition of Ag+ and Zn2+ to DMNS2O caused a new strong emission peak at 420 nm, the emission peak intensity at 600 nm decreased. Two-photon excitation fluorescence spectrum was obtained by excitation at 780 nm.
    研究快报
    An Integrated Microfluidic Chip for Drug-metabolism
    ZHANG Guo-Hao, MA Bo, QIN Jian-Hua, LIN Bing-Cheng*
    2008, 29(7):  1356-1358.  doi:
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    In this paper, we report an integrated microfluidic chip for drug-metabolism. The chip contains three layers: the top PDMS cover, the middle quartz slide with microchannels and microwells, the bottom PDMS layer for cell culture. Microsomes isolated from human liver were encapsulated in microwells by sol-gel method.Using this design, the determination of the metabolites and drug cytotoxicity assessment can be carried out within a single microfluidic device, providing an alternative technique for the high-throughput parallel drug screening and drug interactions in the metabolic pathways.
    研究论文
    Synthesis and Biological Activities of New Neonicotinoids Containing 4-Thiazolidinone
    SUN Xiao-Jun, SU Na, LIU Xing-Hai, DONG Wei-Li, LI Zheng-Ming, ZHAO Wei-Guang*
    2008, 29(7):  1359-1362.  doi:
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    According to bioisosteric relationship and the mode of action between Neonicotinoid compounds and acetylcholin esterase, two series of Neonicotinoid compounds 2-substituted-3-(2-chloro-5-pyridinemethylene)-4-cyanoimino-1,3-thiazolidine(8a—8c) and 5-arylidene-2-aryl-3-(2-chloro-5-pyridinemethylene)-4-thiazolidinones(5a—5e) were designed and synthesized from 4-thiazolidinones(4). Intermediates 4 were synthesized by the condensation of amine, aldehyde and mercapto acetic acid. Their structures were character-ized via elemental analysis, 1H NMR spectra. The preliminary bioassay results show that some title compounds exhibited certain fungicidal activities, promoting cucumber cotyledon root-formation activities and compound 8b showed favourable anti-HIV PR.
    Synthesis and Resolution of Boc-L-Methylphenylalanines
    LI Xiao-Hui1,2*, WANG Guan1, LI Jian-Xun1, XIU Zhi-Long1, NISHINO Norikazu2
    2008, 29(7):  1363-1366.  doi:
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    Synthetic chemists paid great attention on the synthesis of non-natural amino acids due to the improvement in the binding potency, chemical and biological stability and pharmacokinetic characteristics upon introduction of functional groups into peptide based compounds. The methylphenylalanines, the analogs of phenylalanine, play an important role in drug research, such as the drug of anti-hypertension, analogs of enkephalin, the endothelin peptide receptor antagonists and the analogs of hormone. In this paper, o-, m- and p-Boc-L-methylphenylalanines were synthesized using Boc-diethyl malonate and methyl benzylbromide as the starting materials. The racemic amino acids were separated into optical isomers Boc-L-amino acids and Boc-D-amino acid ester by subtilisin. The yields are 42.5%, 47.7% and 64.5%, respectively. In addition, m-L-methylphenylalanine was also prepared using diethyl acetamidomalonate and 2-methyl benzylbromide as the starting materials and the racemic amino acids were separated into optical isomers L-amino acids and Ac-D-amino acids by acylase. The yield is 34.8%. The chemical structures of Boc-L-methylphenylalanines were confirmed by IR, 1H NMR, MS and optical rotation. In comparison of the two methods, the former is simpler, with a higher yield and lower cost. Therefore, it is suitable for industrial application and laboratory preparation.
    Methylation Analysis of Polysaccharide ASP3 from Angelica sinensis(Oliv.) Diels
    SUN Yuan-Lin1,3*, SHEN Rui-Ling2, TANG Jian3, GU Xiao-Hong3
    2008, 29(7):  1367-1370.  doi:
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    The structural features of polysaccharide ASP3 were studied by partial acid hydrolysis and methylation methods, combined with GC-MS instrument. ASP3 was hydrolyzed with 0.2 mol/L trifluoroacetic acid and methylation analysis method were conducted on the samples. The results indicate that the residues of sugar constituents were mainly D-GalpA, D-Galp, L-Araf and L-Rhap. ASP3 contained the main part of homogalacturonan fragments as “smooth regions” with 1,4-D-GalpA and rhamnogalacturonan segments as “hairy regions”. A total of 58.8% Rhap residues in the backbone were substituted at O-4 position by side chains. T-, 1,5-, 1,3,5-Araf and T-, 1,6-, 1,3,6-, 1,4-, 1,4,6-D-Galp were linked as arabinogalactan, galactan and arabinan, which were the mainly constitution of the branch.
    Synthesis and Herbicidal Activities of Novel 1,2,4-Triazolinone Derivatives
    WANG Lei, TANG Mi, LI Wen-Ming, LI Yong-Hong, WANG Su-Hua, LI Zheng-Ming*
    2008, 29(7):  1371-1375.  doi:
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    Several triazolinone compounds such as amicarbazone, azafenidin, sulfentrazone and carfentrazone-ethyl have been developed as herbicides. They are considered to be environment-benign and have a broader application. In order to search for novel 1,2,4-triazolinone derivatives with high herbicidal activities, pyrimidinyl and phenylsulfonyl were introduced to the leading structure. On the basis of the principle of molecular design and structure-activity relationship, twenty-one new 1,2,4-triazolinone derivatives bearing either pyrimidinyl or phenylsulfonyl were designed and synthesized. Their structures were identified by 1H NMR, MS and elemental analysis. The results of preliminary biological activity tests show that some compounds displayed a herbicidal activity at 1.5 kg/ha.
    Thermodynamics and Kinetics Superiorities of 1,4-Dihydronicotinamide as the Activation Center of NADH
    JIAO Xiao-Yun, TAN Yue, ZHU Xiao-Qing*, CHENG Jin-Pei
    2008, 29(7):  1376-1378.  doi:
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    Two series of substituted phenyl-1,4-dihydronicotinamide and their 1,2-dihydroisomers as NADH models were synthesized. The reaction heats and activation parameters of the hydride transfer from the NADH models to N-methylacridinium cation were determined. The results show that the thermodynamic driving force of the hydride transfer from the 1,2-dihydro-NADH models is larger than that of the hydride transfer from the corresponding 1,4-dihydro-NADH models, but the former has quite large positive activation entropy change, which makes the activation free energy change of the former reactions become higher than that of the latter reactions. When the thermodynamics and kinetics on the hydride reverse transfers were examined, the results show that neither thermodynamics nor kinetics are favorable for the hydride transfer to the 2-position of the PNA+, the main reason is that the hydrogen atom has larger steric hindrance at 2-position than that at the 4-position.
    Generation of Selenium-containing Human Single-chain Fv Antibody with GPX Activity
    HUO Rui1,2, SHI Yi1, WEI Jing-Yan1,2*, XU Jun-Jie1, L 2008, 29(7):  1379-1383.  doi:
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    Human single chain fragments variable(scFvs) against GSH were screened from a phage display human scFv antibody library. After three rounds of panning, five clones(2, 11, 16, 24, 32 ) binding to GSH were selected by ELISA. Analysis of PCR products using gel electrophoresis and sequencing showed that three clones(11, 16, 24) contained intact scFv-encoding gene. The scFv-encoding gene from clone 11 was subcloned into the expression vector pPELB and expressed as soluble form(scFv-11) in Escherichia coli Rosetta. The scFv-11 was purified by Ni2+-immobilized metal affinity chromatography. The specificity to GSH of scFv-11 was verified by immuno-dot blot. Selenium-containing human scFv(Se-scFv-11) with GPX activity of 351 U/mol was obtained by the chemical modification of the reactive serine residues into Secs.
    Function Analysis of S160 in 5'UTR of hKv4.3 Gene
    LI Hao1,2, JIANG Chun-Lai1, YU Xiang-Hui1, WU Yong-Ge1, LI Wei1, KONG Wei1*
    2008, 29(7):  1384-1389.  doi:
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    hKv4.3 is the main molecular basis of transient outward K+ current(Ito). Its expression is found in abundance in heart and brain, but with no detectable expression in other tissue. In order to define the gene regulation of hKv4.3 expression, we cloned the sequence(+2—+160, S160) in the 5'UTR of hKv4.3 gene into the report plasmid, and it was transiently expressed. It was found that S160 repressed the activity of promoter of hKv4.3 and SV40, moreover, its repression function with position-specificity but without orientation-specificity. Through the analysis of deletion mutant, we found an repressor element S(GAGGGGTTAA) locating in the downstream region(+20—+30 bp) of TSS. We analyzed mRNA quantity with RT-PCR method, and think that the repressor element S maybe represses the expression in translation level.
    Molecular Modification and Expression of Human CuZn Superoxide Dismutase in pichia pastries
    QU He-Zhi, DU Shan-Shan, HAO Dong-Yun, ZHANG Lei, HUANG Lu, WANG Xiao-Ping*
    2008, 29(7):  1390-1392.  doi:
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    CuZn Superoxide dismutase(CuZn-SOD) is the enzyme that can catalyze the removal of superoxide radicals, which are generated in a variety of biological oxidations. It is a ubiquitous enzyme and provides a defense against oxygen toxicity. To dismutate superoxide radical effectively in and around vascular endothelial cells, we constructed a fusion gene encoding a hybrid SOD(namely HBSOD) consisting of human CuZnSOD and a C-terminal basic peptide that binds to heparin-like proteoglycans. The fusion gene was expressed successfully in pichia pastries. The purified HBSOD exhibited a normal SOD activity. The protein also possessed a high binding affinity to heparin proteoglycans.
    Removal of NO by CH4 Using CuO/TiO2-γ-Al2O3 Catalyst in Combination with Plasma
    LI Hui-Juan, JIANG Xiao-Yuan*, LIN Hui, ZHENG Xiao-Ming*
    2008, 29(7):  1393-1399.  doi:
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    Cu-based catalysts supported on 15%TiO2/γ-Al2O3 carrier, was prepared by precipitation method. BET and XRD results show that the pore size distributions of 15%TiO2/γ-Al2O3 were mainly between micro-pores and meso-pores, and the CuO crystal diffraction peaks were detected, respectively. By using a hybrid system integrating plasma activation and a 12%CuO/TiO2/γ-Al2O3 catalyst, the reactions of NO+CH4+O2 were studied under different conditions including plasma only, catalyst only and plasma with catalyst. It is found that only plasma existed, the NO and CH4 conversion increased with a higher plasma power supply, and the addition of 2.5%O2 increased NO and CH4 conversion. Only when catalysts eristed, the NO and CH4 conversion both increased with the increase of temperature and reached 30% and 20%, respectively. And at the same time, the NO conversion was increased first with O2 content increasing and then decreased, and CH4 conversion was increased with O2 content increasing. When both plasma and catalyst coexisted, the conversion trend of the NO and CH4 with variation of O2 content was consistent with that when only catalyst existed. Besides, the NO conversion was in the range from 15% to 35% and the low temperature NO conversion was obviously increased. For the CH4 conversion, it was increased greatly to 90%.
    An Ultra-concentrated Hydrochloric Acid Model and Palladium Microemulsion Extraction Behavior
    HUANG Kun, XU Yi-Zhuang*, LI Wei-Hong, WENG Shi-Fu, WU Jin-Guang
    2008, 29(7):  1400-1405.  doi:
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    Evolution of the microscopic aggregating structure in the palladium loaded TBP extractive organic phases, with the increase of hydrochloric acid extracted into, was characterized by various spectroscopic techniques. It is indicated that,(1) within the nano-water pools of W/O reversed micelles/microemulsions from TBP equilibrated with higher concentration aqueous HCl solutions, the concentration of acid were far higher than that of saturated concentrated hydrochloric acid. It means an ultra-concentrated hydrochloric acid formed in the nano-water pool; (2) the nanometer-sized confinement brings aggregation of a large amount of H+ and Cl- ions within the micro-droplets, the coordination states of palladium complex ions were changed. It is possible that the hydrated H+ ions participate in the formation of complexes, HmPdClnz+; (3) with respect to various HmPdClnz+ coordination compounds, such as PdCl42-, HPdCl4- and H2PdCl4, their content ratios were different corresponding to the H+ ion concentrations in confined nano-water pools. The acidified TBP molecules have a higher surface activity. The association ability of the acidified TBP molecules with various HmPdClnz+ complexes plays an important role by influencing the palladium extraction behavior.
    Influence of Calcination Temperature on Structure and Adsorption and Photocatalytic Activity of Titanium Oxide Pillared Bentonite
    CHEN Jie, LIU Yan, HUANG Lei, FENG Wei*, XIONG De-Qi
    2008, 29(7):  1406-1411.  doi:
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    TiO2-pillared bentonite(Ti-Na-MMT) was synthesized via acid-catalyzed sol method and the influence of calcination temperature on the structure of Ti-Na-MMT and the removal of azo dye in aqueous solution were analyzed with XRD, FTIR, TG-DTA, BET and DRS. The results show that all the prepared materials were found thermally stable up to 773 K. The d001 basal spacings of Ti-Na-MMT decreased with the increase of the calcination temperature. BET special surface area, median pore diameter, maximum pore volume and the size of titanium of Ti-Na-MMT were related to calcination temperature. BET specific surface area and maximun pore volume of Ti-Na-MMT calcinated at 473 K were the biggest, while median pore diameter and the size of titanium was the smallest. With the increase of calcination temperature, BET surface area and maximun pore volume decreased, while median pore diameter and the size of titanium increased. DRS result shows that Ti-Na-MMT calcinated at 473 K have the strongest absorbency. The regularity of the influence of the calcanating temperature on obsorbtive ability of Ti-Na-MMT was similar with photocatalytic activity, which indicates a synergistic effect on the process of adsorption and photocatalysis. Ti-Na-MMT calcinated at 473 K exhibits the highest adsorptive and photocatalytic activity.
    A Study of the Influence of Cephalosporins on the Microbial Activity of E.coli by Microcalorimetry
    YANG Li-Ni1,2, SUN Li-Xian1, XU Fen1*, ZHAO Zong-Bao3, LIANG Jian-Guo4
    2008, 29(7):  1412-1415.  doi:
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    The effects of Cefoperazone Sodium(CFZ) and Cefoperazone Sodium & Sulbactam Sodium for injection(CFZ-SBT) on the metabolism of Escherichia coli(E.coli) DH5α were studied by microcalorimetry. The microbial activity was recorded as power-time curves through an ampoule method with a TAM air isothermal microcalorimeter at 37 ℃. The parameters such as the growth rate constant(k), inhibitory ratio(I), the maximum power output(Pm) and the time(tm) corresponding to the maximum power output were obtained. The lethal doses of CFZ and CFZ-SBT were calculated as 0.1 and 0.25 μg/mL, respectively. Moreover, according to the relationship between k, Pm, tm and c, the conclusion could be made that the CFZ-SBT cannot improve the inhibitory effect on E.coli DH5α in comparison with the CFZ.
    A Kinetics of Indirect Electro-oxidation Reation of NH3-N with Chloride Ion in a Filter-press Type Electrochemical Cell
    XU Hong1,2, SU Jing1,2, XIAN Xin-Liang1, HUANG Wei-Min1,2, LIN Hai-Bo1,2*
    2008, 29(7):  1416-1419.  doi:
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    Indirect electro-oxidation of the simulated wastewater containing ammonia-N in a filter press-type electrochemical cell was studied. The process obeys a second order reaction kinetics with a certain concentration of chlorine ion, when the concentration of NH3-N is equivalent of/to the one of electro-generated active chlorine. The cell performance is influenced significantly by the operating conditions including current density, flow rate and initial concentration of NH3-N. The results show that the best optimum operating condition is electrolyte flow rate of 60 L/h and current density of 60 mA/cm2 in slightly alkaline(pH=8.0) solution with 0.1 mol/L NaCl and 1 mol/L Na2SO4 as a supporting electrolyte at 25 ℃, and kinetic rate constant k2=3.23×10-5 m3/(mol·s). The information about the spatial distribution of the reactions may be obtained from the Hatta number. The value of the Hatta number(<0.3), estimated under different operation conditions, implies that most of the reaction of the ammonia with active chlorine occurred in the bulk solution, which provided the effective information to design the electrochemical cell.
    Studies on Electrocatalytic Oxidation Mechanism of p-Methylphenol
    TIAN Mei*, YANG Li-Juan, CUI Rui-Hai, ZHANG Heng-Bin, BI Jing
    2008, 29(7):  1420-1423.  doi:
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    Electrocatalytic activity of Ti/PbO2 anode on oxidation degradation of p-methylphenol was studied by linear sweeping voltammetry and galvanostatic electrolysis in an electrolytic cell without diaphragm. Electrocatalytic oxidation mechanism of p-methylphenol was explored by HPLC analysis of p-methylphenol and its degradation intermediates in anodic oxidation processes. The results indicat that Ti/PbO2 electrode can electrocatalyze the oxidation of p-methylphenol and its intermediates in the solution effectively. The conversion of p-methylphenol and the removal ratio of oganic carbon reached 74.31% and 61.8% in 3.0 h, respectively, in the electrolyzing process with constant current 50 mA/cm2 in the solution containig initial concentration 2 mmol/L of p-methylphenol at 25 ℃. The pathway of electrooxidation degradation of p-methylphenol may be p-methylphenol→p-hydroxybenmethanol→p-hydroxybenzaldehyde→p-hydroxybenzoic acid→hydroquinone→benzoquinone→maleic acid→oxalic acid, and the final product is CO2. The electrooxidation reactions of hydroquinone and maleic acid are the rate determining steps.
    Process Investigation of the Electrochemical Fabrication of Au Tunnel Junction with Atomic-scale
    DONG Xiao-Dong1,2, ZHANG Bai-Lin1,2* , XIA Yong1,2, ZHU Guo-Yi1,2
    2008, 29(7):  1424-1427.  doi:
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    A stable Au tunnel junction was fabricated electrochemically with the thin gold wire and the process was investigated in details. It is found that Au tunnel junction is not easy to be obtained by direct electrochemical etching of Au wire due to the mechanical stress. However, it’s easy to control the process of electrochemical deposition on a preformed Au electrode pair as well as its reverse process-etching with addition of chloiroauric acid in solution. The existence of Au ions may cause somewhat instability of the junction, while in hydrochloric acid solution, the process is under control and the Au tunnel junction is stable.
    Fabrication and Characterization of Multicore Superparamagnetic Ni0.5Zn0.5Fe2O4/SiO2 Catalyst Support
    WANG Hong-Xia1,2, ZHANG Fa-Ling1, CAO Yuan2, ZHOU Bo1, LIU Zhi-Guo1, SU Wen-Hui1*
    2008, 29(7):  1428-1431.  doi:
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    A multicore superparamagnetic Ni0.5Zn0.5Fe2O4/SiO2 catalyst support was synthesized by slightly modifying the conventional preparation method, namely, altering the manner of introducing Ni0.5Zn0.5Fe2O4 nanoparticles into TEOS. The modified method resulted in a great increase in specific surface area, saturation magnetization of Ni0.5Zn0.5Fe2O4/SiO2 and better separation in liquid system. The synthesized catalyst supports were characterized by means of X-ray diffraction, N2 gas adsorption-desorption experiments, transmission electron microscopy and a physical properties measurement system(PPMS).
    Studies on the Binding Modes of HIV-1 Integrase with Viral DNA via Molecular Docking Method
    HU Jian-Ping1,2, KE Guo-Tao1, CHANG Shan1, CHEN Wei-Zu1, WANG Cun-Xin1*
    2008, 29(7):  1432-1437.  doi:
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    HIV-1 integrase(IN) integrates the viral DNA into the host cell chromosome, however, the binding mode of IN with the viral DNA and the integration mechanism remain unclear. In this paper, molecular docking method was used to investigate the interactions of HIV-1 IN dimer with the 8 bp and 27 bp segments of viral DNA before the 3’ processing(3’-P) reaction, and the specific binding mode between IN and its substrate 27 bp segments of viral DNA was obtained. The results show that IN has one specific DNA-binding region and another non-specific DNA-binding region. The key residues for IN dimer binding with viral DNA are K14, R20, K156, K159, K160, K186, K188, R199 residues in chain B and K219, W243, K244, R262, R263 residues in chain A. The explanation for the minimum length of 15 bp viral DNA to activate IN was given on the basis of the docked complex structure. Through the analysis of the binding energy, it was found that non-polar interactions are the principal factor favoring the binding between IN and DNA; whereas, the stable association of viral DNA with the key residues are mainly driven by polar interactions. The simulation results basically agree with the experimental data, which provide us with some structural information for the drug design on the basis of the structure of HIV-1 IN.
    Method of Atom-pair Space Distance and Its Application
    ZHANG Qing-You1,2, XU Lu2*
    2008, 29(7):  1438-1442.  doi:
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    In this article, atom-pairs of compounds, which include abundant three-dimensional information of molecules, were calculated. Vertex’s frequency of atom-pairs space distance was applied to describe the frequency of atom pairs, which is better than segment’s frequency of atom-pairs. Molecular similarity matrixes based on the two frequencies of atom-pairs in different distances of segments were calculated, respectively, and then these similarities were taken as the new variables. The mathematical models were built by using multiple regression analysis and artificial neural networks and the results were compared. The results of predictions of the activities of HEPT derivatives in both two frequencies are satisfactory.
    A Theoretical Study on Isomerization Mechanism Between Organorhenium Alkylidene and Alkylidyne Complexes
    BAI Yun, WANG Fu-Dong, WANG Chang-Sheng*
    2008, 29(7):  1443-1447.  doi:
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    A theoretical study on the isomerization mechanism between organorhenium alkylidene and alkylidyne complexes(Me)2(NHR3)Re(=CHR1)(=NR2) and(Me)2(NHR3)Re(≡CR1)(NHR2), where R1,R2, R3=H,Me,But, were carried out with the density functional theory B3LYP method. The optimal structures of the transition states were located and the activation energies were calculated. The calculation results indicate that the intramolecular hydrogen transfer process is kinetically unfavorable because the high activation energies exists whatever the substituent is. The intermolecular hydrogen transfer process between two alkylidene complexes is less favorable either. The hydrogen transfer process between the alkylidene complex and the water molecule is favorable. The most favorable process is the hydrogen transfer process between the alkylidene complex and the chlorine hydride molecule where the chlorine hydride molecule acts as a bridge or a catalyst. The calculation results suggest that the effects of substituents on the reaction barriers of hydrogen transfer processes are almost the same for all the four processes considered in this work. For each process the most preferable substituents are the methyl or t-butyl group for R1, the hydrogen atom for R2, and t-butyl group for R3. The calculation results also show that the additivity exists for the effects of substituents on the barriers of the α-hydrogen transfer reactions.
    Studies on Spectroscopy Character of C6H5N Using Multiconfiguration Second-Order Perturbation Theory
    HOU Chun-Yuan, ZHENG Qing-Chuan, ZHAO Zeng-Xia, ZHANG Hong-Xing*
    2008, 29(7):  1448-1451.  doi:
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    Complete active space self-consistent field(CASSCF) calculations with 6-31g(d,p) basis sets were performed for a dozen of electronic states of nitrate free radical, C6H5N, and its positive and negative ions in C2v symmetry. All calculated states were valence states and their characters were discussed in detail. For all the calculated states, the accuracy of the total energies was improved by including dynamic electron correlation via the multiconfiguration second-order perturbation theory(CASPT2) method. The results suggest that the calculated transitions of 13A2→13A1 and 13A2→13B2 at 4303.1 and 4212.2 kJ/mol are attributed to π(b1)→ny and π(a2)→ny transition, respectively, while those of 13A2→13B1 and 13A2→11B1 at 2634.9 and 2700.4 kJ/mol belong to the mixture of nx→π*(a2) and π(a2)→nx transitions. The ionization energies were obtained in comparison with the photoelectron spectrum(PES) data. These above results are in agreement with the previous experimental data, which is discussed in detail.
    Fabrication of CdS-Nanoparticle/Polystyrene Latex Through the Combined Use of Surface-Initiated ATRP and Gas/solid Reaction
    WANG Zheng, GAO Yuan, WANG Jia-Yu, ZHANG Jun-Hu, YANG Bai*
    2008, 29(7):  1452-1455.  doi:
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    This paper described the fabrication of CdS-nanoparticle/polystyrene latexes through the combined use of surface-initiated atom transfer radical polymerization(ATRP) and gas/solid reaction. The epoxy groups modified polystyrene(PS) latexes were grafted with α-Br groups easily through the reaction between epoxy groups and BMPA in water. And then, Cd(MA)2 was polymerized via surface-initiated ATRP on the surface of α-Br groups modified PS spheres, CdS nanoparticles were formed in situ by bubbling H2S gas. The resulted CdS-nanoparticle/PS latexes take on strawberry-like shapes and presented a strong fluorescence property.
    Synthesis and Degradation of Polyesteramide Based on L-Lactic acid and β-Alanine
    ZHOU Hai1, YUAN Mao-Quan2, YAO Jin-Rong1*, SHAO Zheng-Zhong1
    2008, 29(7):  1456-1460.  doi:
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    Poly(L-lactic acid-co-β-alanine), a novel biodegradable polyesteramide, was produced by direct melting copolymerization with stannous chloride and p-toluenesulfonic acid as the catalyst, and characterized via FTIR, 1H NMR, 13C NMR, GPC and DSC. To optimize the copolymerization conditions, the content of catalyst, copolymerization temperature and time, as well as the feed ratio, were investigated. The results show the copolymers with a high molecular weight could be obtained from the copolymerization process conducted at 180 ℃ for 15 h with 1.5% of stannous complex catalyst under vacuum. The hydrolytic degradation test in PBS(pH=7.2, 37 ℃) indicates poly(L-lactic acid-co-β-alanine) has an excellent degradability, which could provide a potential application in the biomedical field as a drug control released material.
    Application of QCM Technique in the Kinetics Study of Aniline Emulsion Polymerization
    MA Li*, YAN Jun, GAN Meng-Yu, QIU Wei, LUO Lai-Zheng
    2008, 29(7):  1461-1465.  doi:
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    The kinetic behavior of aniline(An) emulsion polymerization using ammonium persulfate(APS) as the initiator in the presence and absence of a constant magnetic field(MF) was discussed via the quartz crystal microbalance(QCM) technique. The experimental results indicate that the reaction rate exhibited first-order with respect to aniline and half-order to APS and dodecylbenzene sulfonic acid(DBSA). The aniline polymerization rate in the presence of a MF was higher than that of aniline polymerization in the absence of a MF. The activation energy obtained under the two conditions were 40.4 and 41.6 kJ/mol, respectively. It is suggested that the QCM technique can provide an efficient way for the kinetic research of An polymerization.
    Properties of O/W Raw Lacquer Emulsion Prepared via Mixed Emulsifier UE20/PVA
    ZHENG Yan-Yu1,2, HU Bing-Huan1, LIN Jin-Huo1*
    2008, 29(7):  1466-1472.  doi:
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    The O/W type raw lacquer emulsion(RLE) was prepared by the mixed emulsifier urushiol-based emulsifier(UE20)/polyvinyl alcohol(PVA). The effects of mass ratio of UE20 to PVA, mixed emulsifier mass fraction(wME), mass ratio of water to raw lacquer, temperature and storage time on the properties of RLE were investigated. The effect of the wME on the diameter of RLE particles were observed via JSM-6380L TEM. The results show that the viscosity of RLE increased with increasing the PVA content. At a low concentration of wME, RLE belonged to pseudoplastic fluids and shear-thinning character was observed. As wME was increased to no less than 10.0%, RLE exhibited swell fluids characteristics and the lower viscosity of RLE was observed. Both the interreaction between RLE particles and the stability of RLE decreased with increasing RLE temperature, similar phenomena was observed with increasing the water content. The orthogonal experiment shows that the main influential factor which affected the stability and viscosity of RLE was wME, secondly mass ratio of water to raw lacquer. With increasing wME, erose particles of RLE translated into sphericity and the diameter of RLE particles decreased.
    Synthesis and Properties of Fluorinated Acrylate Copolymer with Core-shell Structure

    LIANG Jun-Yan, HE Ling*, ZHENG Yuan-Suo

    2008, 29(7):  1473-1478.  doi:
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    The synthesis and characterization of fluorinated acrylate copolymer with core-shell structure was carried out in this paper by the starved semi-continuous seed emulsion polymerization. n-Butyl acrylate(BA) and methyl methacrylate(MMA) served as the non-fluorinated monomers. Trifluoro-ethyl methacrylate(TFEM), hexafluoro-butyl methacrylate(HFBM) and dodecafluoro-heptyl methacrylate(DFHM) served as the fluorinated monomers respectively. The analysis results of FTIR, 1H NMR, TEM as well as DSC indicated that the prepared fluorinated acrylate copolymers were the typical core-shell structure. DSC, TGA, SEM-BSE and SEM-EDX characterizing results displayed that the core-shell copolymer presented an excellent thermal stability and film properties. Fluorinated monomers with a long or short fluorinated side-chain in the copolymer made trivial influence on the thermal stability. However, the long fluorinated side-chain preferentially migrated to the surface during the film formation and benefited the properties of the fluorinated acrylate copolymer.
    Synthesis of Novel H-shaped Block Copolymer by the Combination of Enzymatic-Promoting Ring-opening Polymerization and ATRP
    WANG Di1, ZHANG Bao1, LI Ya-Peng1*, SUN Jing-Hui2
    2008, 29(7):  1479-1482.  doi:
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    Enzymatic-promoting ring-opening polymerization(ROP) of ε-caprolactone(ε-CL) was performed in the presence of biocatalyst Novozyme-435 and initiator ethylene glycol. The resulting polymer was esterified with 2,2-Dichloro acetyl chloride(DCAC) to obtain macroinitiator, which can be used in the following ATRP of the glycidyl methacrylate(GMA) using CuCl/2,2’-bipyridine as the catalyst system to synthesize the well-defined H-shaped block copolymer(PGMA)2-b-PCL-b-(PGMA)2. The structure of the polymer was characterized via GPC and 1H NMR analysis. The polydisperisty of the resulting H-shaped block copolymer is 1.32, Mn=32000. The thermal properties of block copolymer was characterized by differential scanning calorimetry.
    Effect of Different Organo-montmorillonites on Structure and Properties of PP/Montmorillonite Nanocomposite Materials
    JIANG Mei1,3*, FAN Jia-Qi2, WANG Qing-Guo1 , HE Ping2, ZHANG Ming-Yuan1, QI Zong-Neng2, MA Yong-Mei2*, YANG Bai3
    2008, 29(7):  1483-1487.  doi:
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    Organo-montomorillonites with hydroxyl, epoxy and no polar groups were prepared. They were used to prepare PP/clay nanocomposite materials with maleic anhydride-PP as a compatilizer. The structure and the mechanical properties were measured via XRD, TEM, DSC and TGA. The effect of organo-montmorillonite on the structure and properties of PP/clay nanocomposites were studied. The results show that organo-montmorillonite with polar group has a strong affinity to maleic anhydride-PP, it benefits the intercalation and exfoliation of clay and also the increase of degree of crystallization and the mechanical properties.
    Preparation and Properties of Two-layer Integrative Hydrogel as Biomimetic Cartilage Replacement Material
    WANG Ying-Jun1,2*, XU Hong1, ZHENG Yu-Dong3, REN Li1,2
    2008, 29(7):  1488-1491.  doi:
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    Two-layer integrative hydrogels were prepared as biomimetic articular cartilage replacement materials through ultrasonic dispersion, heat-high-pressure, freeze/thawed and radiation technique. The effects of PVP mass fraction and irradiation dose on the gel content, crystallinity structures and elastic compress modulus were investigated. The microstructures of the two-layer integrative hydrogels were also characterized. It was found that the gel content increased with the increase of PVP mass fraction(0—40%) and irradiation dose(0—60 kGy). The crystallinity of PVP-PVA composite hydrogel is the highest under 10 kGy irradiation dose and 20%PVP. Two-layer integrative hydrogel with 20% PVP under 20 kGy irradiation dose showed the highest elastic compress modulus. SEM results show that the surface structures of PVP-PVA composite hydrogels were improved with increasing the PVP mass fraction. SEM results also indicate that the integrative hydrogel showed a good compatibility between top-layer and underlayer. Based on the above results, the two-layer integrative hydrogel showed a promoting prospect as biomimetic cartilage replacement material.
    研究快报
    Synthesis and Characterization of Azido- and Amino-bearing Aliphatic Polyesters
    SHI Quan1,2, CHEN Xue-Si1, HU Xiu-Li1,2, SUN Jing1,2, XIAO Hai-Hua1,2, JING Xia-Bin1*
    2008, 29(7):  1492-1494.  doi:
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    Functionalized aliphatic polyesters, especially those with pendent hydroxyl, carboxyl and amino groups, have attracted much research interest in recent years due to their perfect biocompatibility, biodegra-dability and reactivity. Copolymerization of lactide with functionalized cyclic carbonate monomers proved to be an efficient way to functionalize aliphatic polyesters. However, random co-polyesters with pendent amino groups were seldom reported. This article reported a facile way to prepare aliphatic polyesters with random pendant azido and amino groups via Click reaction.
    Investigation of Degradation Behavior of Polymer on Surface of Film Due to the Existence of Monochromatic X-ray
    YOU Ji-Chun1, LI Xin-Lin2, SHI Tong-Fei1*, SU Zhao-Hui1*, AN Li-Jia1
    2008, 29(7):  1495-1497.  doi:
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    Degradation and its temperature dependence of poly(methyl methacrylate)(PMMA) in the blend film of PMMA/SAN were investigated via in-situ X-ray photoelectron spectroscopy(XPS). The results show that thermal degradation of PMMA takes place at 185, 130, 80 ℃ and even room temperature due to the existence of monochromatic X-ray. Furthermore, the degradation rate depends crucially on the experiment temperature.
    Synthesis of High-Tg Naphthylated Poly(aryl ether ketone)s
    ZHANG Ying, LIU Bai-Jun, ZHANG Yun-He, JIANG Zhen-Hua*
    2008, 29(7):  1498-1500.  doi:
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    A new bisphenol monomer containing a naphthylene group was synthesized via a Friedel-Crafts acylation reaction followed by a demethylation reaction. Naphthylated poly(aryl ether ether ketone)(PANEEK) and naphthylated poly(aryl ether ether ketone ketone)(PANEEKK) were successfully prepared via typical nucleophilic substitution polycondensations. These two polymers exhibited excellent properties including high Tgs(above 190 ℃), good thermal stability, improved solubility, good mechanical property, low dielectric constants(~2.8 at 1 MHz) and low moisture absorptions.
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