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Table of Content

    25 January 2011, Volume 27 Issue 1
    Content
    Cover and Content of Chemical Research in Chinese Universities Vol.27 No.1(2011)
    2011, 27(1):  0. 
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    Articles
    Effects of Co-addition of DBS and PEG on Wetting Performance of TiO2 Film
    QU Yi-chun, JING Li-qiang*, WANG Wen-xin, FU Hong-gang* and LIU Yang
    2011, 27(1):  1-5. 
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    Nanocrystalline anatase TiO2 films with indium tin oxide(ITO) coated glass as the film substrate were fabricated through spin-coating technique. The TiO2 pastes were prepared with sodium dodecylbenzenesulfonate(DBS) modified TiO2 nanocrystals, synthesized by sol-hydrothermal processes in advance, together with different amounts of polyethylene glycol(PEG) macromolecules. The as-prepared films were mainly characterized by ultraviolet-visible (UV-Vis) spectroscopy, field emission scanning electron microscopy(FE-SEM) and water contact angle(WCA) measurement. Effects of the addition of DBS and PEG on the wetting performance of the resulting films and relevant mechanisms were principally investigated. The results show that the as-prepared film displays super-hydrophilic property after co-addition of DBS and PEG although it is not exposed to ultraviolet light prior to the WCA measurement. This appealing result is mainly attributed to the produced micro- and nanometer-scale hierarchical surface structure with uniformly dispersed micro papillae. Each papilla was made up of a great number of TiO2 nanoparticles. The possible formation mechanisms related to the DBS amphiphilic property of the characteristic surface were also suggested. Moreover, the resulting film also exhibits considerable durability in the superhydrophilicity, which is very useful for practical application in self-cleaning, anti-fogging, and bacteria-resistant fields.
    New Inorganic-organic Hybrid Tetravanadate: Preparation, Characterization and Application in Chemically Modified Electrode
    SUN Ying-hua, LI Xiao-ping, MEI Ze-min, ZHU Yu and NIU Li*
    2011, 27(1):  6-10. 
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    A new inorganic-organic hybrid tetravanadate [Co(2,2'-bpy)3]2V4O12·11H2O(1) has been prepared and characterized. X-Ray diffraction study reveals that compound 1 contains classical cluster anions [V4O12]4–, coordinated cations [Co(2,2'-bpy)3]2+ and eleven water molecules, in which an interesting decamer water cluster is formed. The hybrid nanoparticles were firstly used as a bulk-modifier to fabricate a chemically modified paste electrode (1-CPE). The electrochemical behavior and electrocatalysis of 1-CPE have been studied in detail. The results indicate that 1-CPE has a good electrocatalytic activity toward the reduction of bromate in a 0.5 mol/L H2SO4 aqueous solution. 1-CPE shows remarkable stability that be ascribed to the hydrogen bonding interactions between V4O12 cluster and water cluster, which are very important for practical application in electrode modification.
    Low Melting Point and High Stability Polyoxomolybdate-based Ionic Liquids as Photocatalysts
    DONG Tao, CHEN Fa-wang, CAO Min-hua* and HU Chang-wen*
    2011, 27(1):  11-14. 
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    The polyoxometalate-imidazole ionic liquids(POM-ILs) with low melting points at 94.5 and 95.5 °C, [Cnmim]4[Mo8O26](Cnmim=1-alkyl-3-methylimidazolium, n=12,14), have been successfully synthesized and characterized by DSC, single-crystal X-ray diffraction and TGA, etc. The two POM-ILs have relatively high stability with decomposing temperature up to about 347 and 344 °C, respectively. Further photocatalytic performance was mea- sured via the degradation of rhodamine B(RB) in aqueous solution. The experiments show that the conversion reached to 90% after 90 min under UV-light and the degradation efficiency depended on pH value, different dosages and so on. In addition, the catalysts can be recycled for several times without significant loss of activity.
    Magnetic and Transport Properties of Bi0.5Ca0.5–xLaxFe0.3Mn0.7O3(x=0, 0.05, 0.10, 0.15, 0.20, 0.25) Prepared by Molten Salt Method
    DONG Zhong-ping, HU Bin, CHEN Yan, YUAN Hong-ming* and FENG Shou-hua
    2011, 27(1):  15-18. 
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    Polycrystallines Bi0.5Ca0.5–xLaxFe0.3Mn0.7O3(x=0, 0.05, 0.10, 0.15, 0.20, 0.25) were prepared by molten salt method and showed perovskite orthorhombic structure with space group Pnma. The magnetic measurements indicate that the compounds exhibit antiferromagnetic behavior in a temperature range of 4―300 K. The measurements of transport properties suggest that the substitution of La for Ca enhanced the conductivity, and a kink appeared on the curve of temperature dependence of resistivity at 275 K, which is related to the spin-reorientation in the samples.
    New Zincophosphite with Infinite One-dimensional [Zn(HPO3)(H2PO3)]– Chains: Synthesis, Characterizations and Spectral Properties
    WANG Lei, LUO Yan-ling, WEN Yong-hong*, LI Guang-hua and FENG Shou-hua
    2011, 27(1):  19-22. 
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    With dimethylamine as a template, a new one-dimensional zincophosphite (C2H8N)·[Zn(HPO3)(H2PO3)] was prepared under hydrothermal conditions and characterized by single-crystal X-ray diffraction, FTIR spectrametry, elemental analysis, powder X-ray diffraction, and thermogravimetric analysis. The compound crystallized in the Monoclinic space group P2(1)/c, with cell parameters, a=0.78410(9) nm, b=1.54744(2) nm, c=0.81418(1) nm, β=105.8150(1)°, V=0.95049(2) nm3 and Z=4. The connectivity of the ZnO4 tetrahedron and HPO3 pseudo pyramid resulted in inifinite corner-sharing 4-membered ring chains, which were further linked by the protonated amine  molecules to form a 3D structure via hydrogen bonds. To the best of our knowledge, this is the first existence of a zincophosphite with the anionic framework composition of [Zn(HPO3)(H2PO3)]–. The compound exhibits intense photoluminescence at room temperature.
    Matrix Solid-phase Dispersion Extraction of Alkaloids from the Roots of Aconitum kusnezoffii Reichb.
    WEI Wei, LI Xu-wen, SHI Xiao-lei, ZHOU Hong-yu, YANG Rui-jie, ZHANG Han-qi and J
    2011, 27(1):  23-27. 
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    Matrix solid-phase dispersion(MSPD) was developed for the extraction of four alkaloids, including aconitine, mesaconitine, hypaconitine and deoxyaconitine, from the roots of Aconitum kusnezoffii Reichb. The determination of the analyte was carried out by high performance liquid chromatography with UV detection. The alkaline alumina was used as sorbent. The mixture of acetonitrile and water was used as elution solvent. Several extraction parameters, such as type of sorbent, the ratio of sample to solid support material, type of the elution solvent and the volume of the elution solvent were tested. Mean recoveries ranged from 93.16% to 102.73%, with relative standard deviations from 0.27% to 4.17%. With the extraction efficiency and time expenditure taken into account, MSPD extraction should be a comparatively good method.
    Preparation and Electrochemical Characters of Parathion Molecule Imprinted Polymeric Sensors
    HUANG Yong-xing, LIAN Hui-ting, SUN Xiang-ying and LIU Bin*
    2011, 27(1):  28-33. 
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    A sensitive, fast and low-cost molecular imprinted polymeric sensor for quantitative determination of parathion was prepared with chitosan(CS) as function matrix and parathion(PT) as template molecule via constant potential electrochemical deposition. Sensitive response was obtained with a detection limit of 1.0×10–7 mol/L and an excellent recognition for PT was achieved due to the good memory capacity of the sensor. The developed sensor exhibited good fabrication reproducibility and acceptable stability, which provided a new promising tool for pesticide analysis.
    Enantiomeric Separation of Antidepressant Trimipramine by Capillary Electrophoresis Combined with Electrochemiluminescence Detection in Aqueous-organic Media
    YU Cai-xia, YUAN Bai-qing and YOU Tian-yan*
    2011, 27(1):  34-37. 
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    The antidepressant trimipramine(Tri) enantiomers were successfully separated by capillary electrophoresis(CE) coupled with electrochemiluminescence(ECL) detection in aqueous-organic media. A dual cyclodextrin(CD) system combining β-CD and hydroxypropyl-β-cyclodextrin(HP-β-CD) was used as chiral selector. Acetonitrile(ACN) was added to the running buffer to improve the separation efficiency, detection sensitivity and repeatability. The method was also successfully applied to the chiral separation of Tri in spiked human urine sample.
    Qualitative and Quantitative Analysis of Alkaloids in Cortex Phellodendri by HPLC-ESI-MS/MS and HPLC-DAD
    ZHU Shuang-lai, DOU Sheng-shan, LIU Xin-ru, LIU Run-hui*, ZHANG Wei-dong,
    2011, 27(1):  38-44. 
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    A combined method of high performance liquid chromatograph-elecrtrospray-ionization mass spectro- meter(HPLC-ESI-MS/MS) coupled with a photodiode array detector(HPLC-DAD) and principal component analysis(PCA) was applied to the qualitative and quantitative analyses of alkaloids in Cortex Phellodendri(CP) samples, and to the differentiation of two species of CP, Cortex Phellodendri Chinensis(CPC) and Cortex Phellodendri Amurensis(CPA). Twenty-two peaks appeared in the HPLC-MS base peak chromatogram of CP detected by the HPLC-ESI-MS/MS analysis, and the alkaloids were identified according to the MSn data, the known MS fragmentation rules and the literature data. Five alkaloids including berberine, palmatine, jatrorrhizine, phellodendrine and magnoflorine were simultaneously determinated by the HPLC-DAD. Berberine was the primary component in all CP samples, and the contents of berberine and palmatine were exploited to be two critical parameters for effective discrimination between the two species of CP. The average content of berberine in CPC(58.75 mg/g) was higher than that in CPA(9.16 mg/g), while the content of palmatine was less, only 0.25 mg/g in CPC and 4.19 mg/g in CPA. With the use of PCA, samples datasets were separated successfully into two different clusters corresponding to the two species, and berberine, palmatine, phellodendrine and magnoflorine contribute most to the above mentioned calssi- fying. The proposed method proved to be a useful tool in the quality control of Chinese herbal medicines.
    Enantioselective Iodolactonizations of (E)- and (Z)-5-Substituted-4-pentenoic Acid Derivatives Mediated by Chiral Salen-Co(II) Complex
    NING Zhao-lun, DING Jin-ying, JIN Ri-zhe, KANG Chuan-qing, CHENG Yan-qin
    2011, 27(1):  45-48. 
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    A number of salen-metal complexes were prepared and their enantioselective catalytic properties toward the asymmetric iodolactonization of (E)- and (Z)-5-substituted-4-pentenoic acid derivatives were investigated. The catalyst system based on salen-Co(II) complex exhibited moderate to good enantioselectivity with the e.e. value ranging from 53% to 74%, as well as high regioselectivity of δ- vs. γ-iodolactones. The salen-Co(II) complex showed the highest enantioselectivity on the asymmetric iodolactonizations of (Z)-5-substituted-4-pentenoic acid derivatives among these reagent-controlled iodolactonization protocols known so far.
    Synthesis of Spiro Dihydrofurans and 1,8-Dioxo-xanthenes via DABCO Catalyzed Tandem Reaction of Aldehyde with Cyclohexane-1,3-dione and Dimedone
    CHEN Jiao, SHI Jian and YAN Chao-guo*
    2011, 27(1):  49-53. 
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    The 1,4-diazabicyclo[2.2.2]octane(DABCO) catalyzed reaction of cyclohexane-1,3-dione or dimedone with various aldehydes in acetonitrile resulted in the polysubstituted tetraketones, spiro dihydrofurans or 1,8-dioxo-xanthenes derivatives as main products respectively according to the structure of reactants and reaction conditions.
    Design, Synthesis and Biological Evaluation of 2-Aroyl-3-aryl-6,7-dihydro-5H-furo[3,2-g]chromen Derivatives as a Novel Series of Estrogen Receptor Modulators
    WANG Shi-hui, WANG Yan, ZHU Yu-ying, LIU Si-jie, HAN Jian, ZHOU Yi-fan, LI
    2011, 27(1):  54-59. 
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    Based on the principles of the bioisosterism, combination of the active substructures of selective estrogen receptor modulators which are currently therapeutic agents available for the prevention and treatment of various estrogen dependent diseases, and structural optimization, a novel series of 2-aroyl-3-aryl-6,7-dihydro-5H-furo[3,2-g]-chromen derivatives was designed as potent selective estrogen receptor modulators via molecular docking. The target compounds have been synthesized, and characterized by IR, proton NMR, ESI-MS, elemental analysis and evaluated for their antitumor activity against human osteosarcoma U2OS-EGFP-4F12G cell line. Some target compounds showed good inhibition effects on U2OS-EGFP-4F12G cell line and the preliminary structure-activity relationships were discussed.
    Synthesis and Herbicidal Activity of Novel Sulfonylurea Derivatives
    CAO Gang, WANG Mei-yi*, WANG Ming-zhong, WANG Su-hua, LI Yong-hong and LI Z
    2011, 27(1):  60-65. 
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    Sulfonylurea herbicides have been applied worldwide in agriculture. Some sulfonylurea residues might exist in soil longer than that people expected. However, flupyrsulfuron-methyl-sodium which was firstly reported as a new 5-substituted sulfonylurea herbicide has less than one month residual life. Therefore, 5-substituted benzenesulfonylureas are potential molecules to regulate its residual situation. In order to develop new sulfonylurea derivatives, the substituent on the critical 5-posotion of the benzene ring was optimized. On the basis of our former work on sulfonylureas which contains a characteristic mono-substituted pyrimidine moiety, twenty-six new sulfonylurea derivatives were synthesized and their structures were confirmed by 1H NMR, 31P NMR and elemental analysis. The greenhouse bioassay tests show that some title compounds exhibit potent herbicidal activity.
    Novel Method for Synthesis of Diarylpyrazole Derivatives as Cannabinoid CB1 Receptor Antagonists
    WU Ying-qiu, ZHENG Guo-jun, WANG Ya-ping, WANG Xiang-jing and XIANG Wen-sheng
    2011, 27(1):  66-69. 
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    A novel and efficient method was developed for the synthesis of diarylpyrazole derivatives as cannabinoid CB1 receptor antagonist via four step reactions. The key step was the synthesis of a diarylpyrazole skeleton, which involved initial condensation of the sodium salt of compound 12 with diazonium compounds, and further cyclization by heating at reflux in acetic acid. Eight diarylpyrazole derivatives and nine new synthesized compounds were characterized by 1H NMR, IR, MS, and elemental analysis. The reaction conditions were mild and the overall yields of the target compounds ranged from 26% to 44%.
    MicroRNA-mediated Silencing of RhoC Inhibits Tumor Invasion and Increases Chemosensitivity to Paclitaxel in SKOV3 Cells in vitro
    PAN Ying, DU Zhen-wu, LENG Wei-chun, ZHOU Jia-wen, WANG Ying-jian, SHENG Min-jia
    2011, 27(1):  70-74. 
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    RhoC is a member of the Ras-homologous family of genes which are implicated in tumorigenesis and tumor progression. Up-regulation of RhoC is associated with tumor progression in ovarian carcinoma and RhoC is significantly correlated with the invasive capability of ovarian cancer cell lines in vitro. We developed a system   that blocks RhoC in the human ovarian cancer SKOV3 cells using specific MicroRNA(miRNA) interference. By transfecting  SKOV3 cells with the plasmid vector to express specific MiRNA that targets human RhoC, we were able to establish a stable clone in which RhoC expression was significantly downregulated. This resulted in the decreased invasive potential of SKOV3 cells as well as increased chemosensitivity to paclitaxel. RhoC involves in  invasion and chemosensitivity of SKOV3, indicating that RhoC may be a promising therapeutic target for ovarian cancer.
    Antioxidative Capacity of Irbesartan
    WANG Mei-xue, ZHAO Xue-zhong*, GAI Chun-yu, LIU Hong-min, XU Yan-ping and LI
    2011, 27(1):  75-79. 
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    The author investigated the antioxidant effect of irbesartan[2-butyl-3-({4-[2-(2H-1,2,3,4-tetrazol-5-yl)·phenyl]phenyl}methyl)-1,3-diazaspiro[4.4]non-1-en-4-one], an angiotensin receptor blocker(ARB), on the oxidation of erythrocytes induced by 2,2-[azobis(2-amidinopropane) hydrochloride](AAPH) and H2O2. The value of half concentration(IC50) of irbesartan to scavenge radicals was measured by reacting it with 2,2-[azinobis(3-ethylbenzothia- zoline-6-sulfonate) radical cation](ABTS+·). Activities of the catalase(CAT), superoxide dismutase(SOD), glutathione peroxidase(GSH-Px) and the content of malondialdehyde(MDA) in liver tissue and blood serum of normal-rats were measured by means of spectrophotometry to study the antioxidation function of irbesartan. Results of experiments show that irbesartan can scavenge ABTS+· and superoxide radicals effectively as well as inhibit AAPH-, H2O2-induced hemolysis of erythrocytes. Irbesartan can also increase the activities of GSH-Px, SOD, CAT and   decrease the content of MDA of normal rats. So irbesartan is a good antioxidant.
    Association of Matrix Metalloproteinase-9 and p53 Gene Polymorphisms with Genetic Susceptibility to No-small-cell Lung Cancer
    ZHAO Ying-hao, MA Tong-hui, ZHENG Yong-chen, ZHANG Kun, YANG Jing-bo, YANG
    2011, 27(1):  80-82. 
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    Matrix metalloproteinase-9(MMP-9) and p53 genes play an essential role in the multi-step process of tumorigenesis in lung cancer. Single nucleotide polymorphisms(SNPs) of MMP-9 and p53 genes are associated with the risk and progression of many cancers. In this study, we evaluated the association of the R279Q polymorphism of MMP-9 or the A1/A2 polymorphism of p53 gene with the risk of no-small-cell lung cancer(NSCLC) in Han population of Northeast China. We examined the frequency of SNPs in the two kinds of genes of 50 patients with NSCLC and 50 cancer-free controls frequency-matched by age and sex. Polymerase chain reaction-restriction fragment length polymorphism(PCR-RFLP) technique was used to determine the genotypes. The results indicate that the 279RR genotype in MMP-9 gene and the A1/A2 genotype in p53 gene show a significantly increased risk of NSCLC. Therefore, the MMP-9 279RR and p53 A1/A2 genotypes may be used as markers for susceptibility to NSCLC in Han population of Northeast China.
    Primary Research of Immunological Mechanism of Combined Hepatitis A-Measles-Varicella Vaccine
    LI Ying-hua, GUAN Feng, ZHANG Xi-zhen, ZHAO Hong-guang, LIU Jing-ye, LIN Ch
    2011, 27(1):  83-86. 
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    To explore the primary humoral and cellular immunological mechanism of the combined hepatitis A-measles-varicella vaccine, the mice were inoculated with hepatitis A-measles-varicella vaccine by intraperitoneally and two weeks later, blood was collected to observe the mice’s immunological status. Antibody level was measured to appraise the humoral immunity. At the same time, T lymphocyte surface marker, NK cell activity, LAK cell activity, delayed type hypersensitivity of skin, Mφ phagocytic function, mRNA level of cytokine IL-2 and IFN-γ plus lymphocyte transformation test were used to analyze the cellular immunity. The humoral immunity results show that the combined hepatitis A-measles-varicella vaccine produce the same antibody level as their corresponding univalent vaccine, and maintained fine immunogenicity and security. The result of cellular immunity shows that the combined vaccine could activate physical immunocyte, increase the regulative ability of cytokine,enhance the physical immune function and immune defense ability. The present research proved the security and better humoral and cellular immunity of combined hepatitis A-measles-varicella vaccine from the immunological point of view, which laid good foundation for further study and development.
    Identifying Metabolite and Protein Biomarkers in Unstable Angina In-patients by Feature Selection Based Data Mining Method
    SHI Cheng-he, ZHAO Hui-hui, HOU Na, CHEN Jian-xin, SHI Qi, XU Xue-gong, WA
    2011, 27(1):  87-93. 
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    Unstable angina(UA) is the most dangerous type of Coronary Heart Disease(CHD) to cause more and more mortal and morbid world wide. Identification of biomarkers for UA at the level of proteomics and metabolomics is a better avenue to understand the inner mechanism of it. Feature selection based data mining method is better suited to identify biomarkers of UA. In this study, we carried out clinical epidemiology to collect plasmas of UA in-patients and controls. Proteomics and metabolomics data were obtained via two-dimensional difference gel electrophoresis and gas chromatography techniques. We presented a novel computational strategy to select biomarkers as few as possible for UA in the two groups of data. Firstly, decision tree was used to select biomarkers for UA and 3-fold cross validation was used to evaluate computational performances for the three methods. Alternatively, we combined independent t test and classification based data mining method as well as backward elimination technique to select, as few as possible, protein and metabolite biomarkers with best classification performances. By the method, we selected 6 proteins and 5 metabolites for UA. The novel method presented here provides a better insight into the pathology of a disease.
    Effects of Hydroxyapatite Nanoparticles on Apoptosis and Invasion of Human Renal Cell Carcinoma 786-0 Cells
    WANG Zhi-xin, HOU Yi, HAN Wei, WANG Kai-chen, GUO Bao-feng, LIU Ying, CHAN
    2011, 27(1):  94-98. 
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    Renal cell carcinoma is the most common cancer of the kidney, and resistant to traditional therapies. The aim of this study is to investigate the effects of hydroxyapatite nanoparticles on human renal cell carcinoma 786-0 cells. Cell proliferation was assessed with an 3-(4,5-dimethylthiazol-2-yl) 2,5-diphenyltetrazolium bromide(MTT) staining kit. The apoptosis assay was assessed with an FITC Annexin V Apoptosis Detection Kit. Caspase-3 and caspase-12 were detected by immunocytochemical staining and semi-quantitative RT-PCR. Cell wound healing assay was used to ensure cell motility. Matrigel invasion assay was analysed via transwell chambers. Our results showed that hydroxyapatite nanoparticles significantly reduced cell proliferation, invasion and induced apoptosis of 786-0 cells. The inhibiting action may have relation with up-regulated caspase-12, leading the cells to apoptosis. This study suggests that hydroxyapatite nanoparticles may be an effective and delivery system for renal cell carcinoma therapy.
    Aquaporin 1 Facilitated Hepatocellular Carcinoma SMMC7221 Cell Migration Associated with Water Permeability
    ZHANG Ai-li, LI Jiang, WANG Yan-qing, ZAKNROU Zohra, MA Tong-hui and LI X
    2011, 27(1):  99-103. 
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    The authors investigated the regulation of human aquaporin 1(hAQP1) and the involvement of aquaporin 1(AQP1) in the migration of human hepatocellular carcinoma SMMC-7221 cells using RNA intereference technology. Firstly, two short hairpin RNA(shRNA) constructs in PBSU6 vector were reconstructed and their knockdown effects were identified in SMMC-7221 cells. Next, the involvement of endogenous hAQP1 in regulating the migration of SMMC-7221 cells was investigated via siRNA technology. HAQP1-shRNA can specifically inhibit AQP1 dependent osmotic water permeability. Meanwhile the migration of SMMC-7221 cells was inhibited remarkably after silencing AQP1 by performing transwell cell migration assay and in vitro wound healing assay. Furthermore, in the presence of an inhibitor HgCl2, the water permeability of the cell membrane was remarkably decreased, the expression of AQP1 was upregulated after HgCl2 treatment and the cell movement was decreased at the moment. Increased AQP1 cannot attenuate cell migration ability when cell membrane loses its water permeability function. This demonstrates that the cell migration was remarkably related to the transporting water function of cell membrane.
    Structural Analysis of an Oligosaccharide and Glycopeptide Mixture from Panax Ginseng Root with Inhibition SHP-1 Function
    WANG Ying, GAO Qi-pin, LI Gui-rong, CHEN Ying-hong, LUO Hao-ming, GAO Yang
    2011, 27(1):  104-107. 
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    A mixture of oligosaccharide and glycopeptide was isolated from the aqueous extract of Panax ginseng roots. The mixture inhibits protein tyrosine phosphatase(SHP-1) function, implying it enhances immune activity. The peak molecular mass of the oligosaccharide portion is 1800 calculated via GPC software after separation by HPLC. And the structure of the oligosaccharide portion is the backbone of (1→3)- and (1→4)-linked arabinopyranoside, and (1→4)- and (1→6)-linked glucopyranoside, with non-reducing terminals of arabinopyranoside and glucopyranoside. The peak molecular mass of glycopeptide portion is 1900 calculated via GPC software after separation by HPLC. The structure of glycopeptide portion is the backbone of (1→3)- and (1→4)-linked arabinopyranoside, and (1→3,6)-linked glucopyranoside, with non-reducing terminals of galactopyranose and glucopyranoside. The peptide composition is Glu, Asp, Hyp, Ser, Arg, Gly, Thr, Pro, Ala, Val, Ile, Leu and Lys. The oligosaccharide-peptide linkage is formed by Ara and Hyp.
    Prediction of RNA Secondary Structure Based on Particle Swarm Optimization
    LIU Yuan-ning, DONG Hao, ZHANG Hao*, WANG Gang, LI Zhi and CHEN Hui-ling
    2011, 27(1):  108-112. 
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    A novel method for the prediction of RNA secondary structure was proposed based on the particle swarm optimization(PSO). PSO is known to be effective in solving many different types of optimization problems and known for being able to approximate the global optimal results in the solution space. We designed an efficient objective function according to the minimum free energy, the number of selected stems and the average length of selected stems. We calculated how many legal stems there were in the sequence, and selected some of them to obtain an optimal result using PSO in the right of the objective function. A method based on the improved particle swarm optimization(IPSO) was proposed to predict RNA secondary structure, which consisted of three stages. The first stage was applied to encoding the source sequences, and to exploring all the legal stems. Then, a set of encoded stems were created in order to prepare input data for the second stage. In the second stage, IPSO was responsible for structure selection. At last, the optimal result was obtained from the secondary structures selected via IPSO. Nine sequences from the comparative RNA website were selected for the evaluation of the proposed method. Compared with other six methods, the proposed method decreased the complexity and enhanced the sensitivity and specificity on the basis of the experiment results.
    Photonic Bandgap Properties of Atom-lattice Photonic Crystals in Polymer
    REN Lin, WANG Dian, SUN Gui-ting, NIU Li-gang, YANG Han* and SONG Jun-feng*
    2011, 27(1):  113-116. 
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    The present paper covers the various photonic crystals(PhCs) structures mimicking real atom-lattice structures in electronic crystals by using the femtosecond laser-induced two-photon photopolymerization of SU-8  resin. The bandgap properties were investigated by varying the crystal orientations in <111>, <110> and <100> of diamond-lattice PhCs. The photonic stop gaps were present at λ=3.88 μm in <111> direction, λ=4.01 μm in <110> direction and λ=5.30 μm in <100> direction, respectively. In addition, defects were introduced in graphite-lattice PhCs and the strong localization of photons in this structure with defects at λ=5 μm was achieved. All the above work shows the powerful capability of femtosecond laser fabrication in manufacturing various complicated three-     dimensional photonic crystals and of controlling photons by inducing defects in the PhCs samples.
    Theoretical Investigation on Hyperfine Structures of Perfluoropolyether Radicals
    DONG Su-li and LIU Ya-jun*
    2011, 27(1):  117-122. 
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    The geometries of CF3OCF2·, CF3OCFCF3· and CF3OCF2CF2· radicals were investigated by density functional theory(DFT) method. The calculated results indicate that all the three radicals have pyramidal shapes at their centers, and the αC is one top of the pyramids. Based on the DFT optimized geometries, the hyperfine coupling constants(hfcc’s) of the 19F atoms of the three radicals were calculated by B3LYP, MP2(full) and QCISD(full) methods. The calculated values agree with the experimental values, especially for the a values of Fα, the a values are 125.6×10–4, 104.2×10–4, and 83.2×10–4 T of CF3OCF2·, CF3OCFCF3· and CF3OCF2CF2·, respectively. These results better explain the experimental observation.
    Heterotactic Enthalpic Interactions of L-Arginine with 2,2,2-Trifluoroethanol in Aqueous Solutions at 298.15, 303.15 and 310.15 K
    ZHU Yan*, PANG Xian-hong and YU Li
    2011, 27(1):  123-126. 
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    The enthalpies of mixing of L-arginine with 2,2,2-trifluoroethanol and their respective enthalpies of dilution in aqueous solutions at 298.15, 303.15 and 310.15 K were determined as a function of the mole fraction by flow microcalorimetric measurement. These experimental results were analyzed to obtain heterotactic enthalpic interaction coefficients(hxy, hxxy, hxyy) according to the McMillan-Mayer theory. The hxy coefficients between L-arginine molecule studied and 2,2,2-trifluoroethanol molecule in aqueous solutions at 298.15, 303.15 and 310.15 K were found to be all negative. The results were discussed in terms of solute-solute interaction and solute-solvent interaction.
    Terpyridine-derived Zn2+ Selective Fluorescence Sensor: Ratiometric Fluoroionophoric Behavior Study
    SONG Peng, SUN Shi-guo, ZHOU Pan-wang, LIU Jian-yong*, XU Yong-qian and PENG Xiao-jun
    2011, 27(1):  127-131. 
    Abstract ( )   PDF (354KB) ( )  
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    A sensitive and selective zinc ion ratiometric fluorescence sensor has been synthesized and characterized. This material displays dual fluorescence. After the material was bonded to a closed-shell metal ion, such as Zn2+, the recovery of the local excited fluorescence of the material-Zn2+ complex, largely at the expense of the intramolecular charge transfer fluorescence, is consistent with the difference between selected orbital transitions of the free dye and the metal-chelated complex. For instance, the contribution of the πtpy→πtpy* transition becomes more prominent. This is also consistent with the results of the fluorescence decay behavior, measured via a time-correlated single photon counting setup. In contrast, the corresponding open shell Ni2+-bound complex quenches both kinds of photoluminescence, due to spin-orbit coupling.

    Tb(III) Transport in Dispersion Supported Liquid Membrane System with D2EHPA as Carrier in Kerosene
    PEI Liang*, YAO Bing-hua, WANG Li-ming and MA Zhan-ying
    2011, 27(1):  132-139. 
    Abstract ( )   PDF (290KB) ( )  
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    The transport of Tb(III) in dispersion supported liquid membrane(DSLM) with polyvinylidene fluoride membrane(PVDF) as the support and dispersion solution including HCl solution as the stripping solution and di(2-ethylhexyl) phosphoric acid(D2EHPA) dissolved in kerosene as the membrane solution, has been studied. The effects of pH value, initial concentration of Tb(III) and different ionic strength in the feed phase, volume ratio of membrane solution to stripping solution, concentration of HCl solution, concentration of carrier, different stripping agents in the dispersion phase on the transport of Tb(III) have also been investigated, respectively. As a result, the optimum transport conditions of Tb(III) were obtained, i.e., the concentration of HCl solution was 4.0 mol/L, the concentration of D2EHPA was 0.16 mol/L, the volume ratio of membrane solution to stripping solution was 30:30 in the dispersion phase and pH value was 4.5 in the feed phase. Ionic strength had no obvious effect on the transport of Tb(III). Under the optimum conditions, the transport percentage of Tb(III) was up to 96.1% in a transport time of  35 min when the initial concentration of Tb(III) was 1.0×10–4 mol/L. The diffusion coefficient of Tb(III) in the membrane and the thickness of diffusion layer between feed phase and membrane phase were obtained and the values were 1.82×10–8 m2/s and 5.61 μm, respectively. The calculated results were in good agreement with the literature  data.
    Compatibilization of PBT/PP Blends by Adding Side-chain Liquid Crystalline Ionomer with Quaternary Pyridinium Groups
    XU Xin-yu*
    2011, 27(1):  140-144. 
    Abstract ( )   PDF (513KB) ( )  
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    A side-chain liquid crystalline ionomer(SLCI) was synthesized by grafting copolymerization of 4-(4-ethoxybenzoyloxy)-4′-allyloxybiphenyl and N-allyl-pyridium bromide on polymethylhydrosiloxane. The SLCI was blended with polypropylene(PP) and polybutylene terephthalate(PBT) by melt mixing. The thermal behavior, liquid crystalline properties, morphological structure, and mechanical properties of the blends were investigated by differential scanning calorimetry(DSC), polarizing optical microscopy(POM), scanning electron microscopy(SEM), and tensile measurement. When a proper amount of SLCI was added, fine configurations were formed in the PBT/PP/SLCI blend system, and the mechanical properties were improved due to improved adhesion at the interface. When excess SLCI was added, an inhomogeneous structure resulted, which caused the mechanical properties to deteriorate.
    Photoinitiating Characteristics of Benzophenone Derivatives as Type II Macromolecular Photoinitiators Used for UV Curable Resins
    CHENG Liang-liang, ZHANG Yong and SHI Wen-fang*
    2011, 27(1):  145-149. 
    Abstract ( )   PDF (291KB) ( )  
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    Dodecyl-benzophenone(DBP) and hexadecoxyl-benzophenone(HDBP) as type II photoinitiators used for radical photopolymerization systems were synthesized by Friedel-Crafts reaction, and characterized by 1H NMR and FTIR spectroscopy. The UV-Vis absorption spectra of DBP and HDBP, propitious to photopolymerization under a commercial mercury UV bulb are centered at 345 and 335 nm, respectively. HDBP has higher extinction coefficient than DBP, but lower photoinitiating efficiency. Their photoinitiating performances for EB605, a bisphenol A epoxy acrylate with 40%(mass fraction) tripropyleneglycol diacrylate (TPGDA), resin consisting of bisphenol A epoxy acrylate and tripropyleneglycol diacrylate in the presence of triethanolamine as a coinitiator were investigated by photo-differential scanning calorimetry(photo-DSC). DBP initiates the curing of acrylate more efficiently than HDBP, showing higher photopolymerization rate and unsaturation conversion, resulted from the poor compatibility of HDBP with the resin. The photoinitiating activity of DBP to epoxy acrylate resin is even higher than that of BP at lower loadings.
    Mushroom-shaped Morphology Formed in Thin Films of Cylinder-forming Block Copolymer
    GONG Yu-mei*, SONG Jing-chuan and ZHANG Gui-xia
    2011, 27(1):  150-153. 
    Abstract ( )   PDF (526KB) ( )  
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    The morphology of the film of polystyrene-block-poly(methyl methacrylate)(PS-b-PMMA) block copolymer having polystyrene(PS) cylinder forming composition spin-coated on a neutral brush modified silicon substrate has been investigated in this report. A mushroom-shaped morphology formed in the film with one period to two periods(L0―2L0) in thickness, which was spin-coated under a low humidity condition(RH ca.13%) and then thermally annealed at an extreme high temperature(230 °C). The results suggest that the spin-coating condition together with the confinement conditions plays a crucial role in the interesting morphology formation.
    Determination of Crosslinking and Grafting in Polyurethane-acrylic Hybrid Material and Their Theoretical Calculations
    JIANG Xu-bao, ZHU Xiao-li, ZHANG Zhi-guo, KONG Xiang-zheng* and TAN Ye-bang
    2011, 27(1):  154-157. 
    Abstract ( )   PDF (134KB) ( )  
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    A theoretical method to calculate the mode of polyurethane(PU) prepolymers grafted to polyacrylic(PAC) was presented. Using hydroxyethyl acrylate(HEA) as coupling agent, polyurethane-acrylics(PU-AC) hybrid latexes were prepared with varying HEA level and the reaction of HEA with PU prepolymers at different temperatures, and PU grafted to PAC was experimentally determined. The results show that PU grafted to PAC regularly increased, and the non-grafted and linear free PU regularly decreased with increase in HEA/NCO(isocyanate group). The grafted PU on PAC was not proportional to HEA. More than half of linear PU prepolymers were grafted to PAC when HEA was at a low level with HEA/NCO at 0.33. While grafted PU increased to 84.80%(mass fraction), when HEA/NCO increased to 1.0. The results were interpreted based on the theoretical calculation of PU grafted to PAC by the present method.
    Preparation and Characterization of Nano-Se/Silk Fibroin Colloids
    HOU Ju-ying, AI Shi-yun* and SHI Wei-jie
    2011, 27(1):  158-160. 
    Abstract ( )   PDF (263KB) ( )  
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    A solution-phase approach to the synthesis of nano-Se/silk fibroin colloids(NSeSFC) by reducing selenious acid solution with silk fibroin(SF) was proposed, and the composites were in situ prepared by macrowave method. The nanocomposites were characterized with ultraviolet-visible(UV-Vis) absorption spectrometry, resonance Rayleigh scattering(RRS) spectrometry and transmission electron microscopy(TEM). The nano-Se(0) solution exhibited the strongest resonance Rayleigh scattering at 579 nm. Through the RRS discussion, we found the best preparation and conservation?condition of NSeSFC. The TEM image shows the sizes of the Se(0) particles were about 50 nm and dispersed equably. The resulted NSeSFC exhibited good stability, and it can be kept for a long period.
Editor-in-Chief:
Jihong YU
ISSN 1005-9040
CN 22-1183/O6
Special Issue/Column
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