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    01 February 2014, Volume 30 Issue 1
    Content
    Cover and Content of Chemical Research in Chinese Universities Vol.30 No.1(2014)
    2014, 30(1):  0-0. 
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    Letters
    A Novel 3D Metal Organic Framework Based on an Azolate Ligand
    YIN Xinbo, AN Tiance, WANG Yang, ZHANG Lijuan
    2014, 30(1):  1-3.  doi:10.1007/s40242-014-3501-8
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    Metal organic frameworks (MOFs) constructed from metal ions and organic ligands have been investigated greatly due to the variety of the MOF structures. Azolate type ligands are used frequently to synthesize MOFs to make zeolitic imidazolate frameworks (ZIFs) with high stabilities. We synthesize a 3D MOF {[Zn(BBI)(MSM)(DMSO)]n, H2BBI = benzo-bis (imidazole), MSM = methylsulfonylmethane, DMSO = dimethyl sulfoxide}, constructed from tetrahedral Zn(II) and four-coordinated BBI ligand, with 11.27 ? 1D pore size. In this framework, considering Zn(II) as the vertex, and the BBI together MSM as the edge, dmp topology is obtained.

    Synthesis, Photophysical Properties and TD-DFT Calculation of Fluorescent Dyes Based on Pyrenylthiazoles
    TONG Dingyi, DUAN Haifeng, WANG Jiajun, ZHANG Li, CAO Jungang, WEI Zhonglin, LIN Yingjie
    2014, 30(1):  4-8.  doi:10.1007/s40242-014-3467-6
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    By the easy synthesis, we introduced thiazole to pyrene , thus developing a new class of fluorescent dyes. Then we studied the fluorescence and UV/Vis properties of these dyes. In the single crystal structure, an extraordinary arrangement was found. And these results were in good agreement with theoretical (TD-DFT) calculations.

    Articles
    Solvothermal Synthesis, Crystal Structure and Photoluminescent Property of a Novel 3D [Ca2(HCOO)2(nds)(H2O)2]n
    WANG Shuang, ZHANG Renchun, WANG Junjie, SHEN Lanlan, ZENG Ying, ZHANG Daojun
    2014, 30(1):  9-12.  doi:10.1007/s40242-014-3414-6
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    A novel calcium(Ⅱ) metal-organic framework [Ca2(HCOO)2(nds)(H2O)2]n(1) with mixed 1,5-naphthalene-disulfonate sodium salt(1,5-nds) and formate as organic ligands has been obtained under solvothermal conditions. It was found that the μ3-η2:η2 bridging mode of HCOO- in compound 1 is uncommon. Moreover, the formate, which was in situ formed from N,N'-dimethylformamide, played an important role in the formation of 3D structure. HCOO- ligands bridged Ca(Ⅱ) ions into grid-like layers that were further pillared by the 1,5-nds ligand to form a 3D Ca-based framework. Compound 1 also exhibits a strong blue luminescence at room temperature.

    Metal-organic Chemical Vapor Deposition of GaSb/GaAs Quantum Dots:the Dependence of the Morphology on Growth Temperature and Vapour Ⅴ/Ⅲ Ratio
    YANG Haoyu, LIU Renjun, LÜ You, WANG Liankai, LI Tiantian, LI Guoxing, ZHANG Yuantao, ZHANG Baolin
    2014, 30(1):  13-17.  doi:10.1007/s40242-014-3342-5
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    GaSb quantum dots have been widely applied in optoelectronic devices due to its unique electrical and optical properties. The effects of metal-organic chemical vapor deposition(MOCVD) parameters, such as growth temperature and vapour Ⅴ/Ⅲ ratio[Ⅴ/Ⅲ ratio means the molar ratio of trimethylgallium(TMGa) and triethylantimony(TESb)], were systematically investigated to achieve GaSb quantum dots with high quality and high density. The features of surface morphology of uncapped GaSb quantum dots were characterized by atomic force microscope(AFM) images. The results show that the surface morphologies of quantum dots are strongly dependent on growth temperature and vapour Ⅴ/Ⅲ ratio. GaSb quantum dots with an average height of 4.94 nm and a density of 2.45×1010 cm-2 were obtained by optimizing growth temperature and Ⅴ/Ⅲ ratio.

    Fabrication, Characterization and Optical Properties of TiO2 Nanotube Arrays on Boron-doped Diamond Film Through Liquid Phase Deposition
    YUAN Jüjun, LI Hongdong, WANG Qiliang, CHENG Shaoheng, ZHANG Xianke, YU Huajun, ZHU Xiurong, XIE Yingmao
    2014, 30(1):  18-22.  doi:10.1007/s40242-014-3320-y
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    TiO2 nanotube(TiNT) arrays were deposited on boron-doped diamond films by a liquid-phase deposition method with ZnO nanorod arrays as the template. The different morphologies of TiNTs have been obtained by controlling the morphology of ZnO template. The X-ray diffraction and energy-dispersive X-ray analysis show that the ZnO nanorod array template has been removed in the TiNTs formation process. The crystalline quality of the TiNTs is improved by increasing the annealing temperature. The band gap of the TiNTs is about 3.25 eV estimated by the UV-Vis absorption spectroscopy, which is close to the value of bulk TiO2. In the photoluminescence spectrum, a broad visible emission in a range of ca. 550—750 nm appears due to the surface oxygen vacancies and defects.

    High-efficient Isolation of Plant Viral RNA via TMAOH-modified Fe3O4 Magnetic Nanoparticles
    TANG Yan, ZHAO Xiaoli, CHU Linya, SUN Ning, LIU Renxiao, DENG Congliang, GE Guanglu
    2014, 30(1):  23-26.  doi:10.1007/s40242-014-3269-x
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    Magnetic nanoparticles show great potential in RNA enrichment and separation for rapid detection of viral infection. Fundamental studies on the interaction between RNA and nanoparticles with uniform size and surface property are necessary for designing better adsorbent and optimizing the conditions. In this study, monodispersed superparamagnetic magnetite(Fe3O4) nanoparticles were synthesized by thermal decomposition and modified with tetramethylammonium hydroxide[N(CH3)4OH, TMAOH] that become highly dispersible and stable in water. High-efficiency plant viral RNA adsorption onto TMAOH/Fe3O4 nanoparticles in the extracted solution of plant leaves was demonstrated. The changes of surface charge of TMAOH on the Fe3O4 nanoparticles with pH contribute to the RNA adsorption and elution. Separating viral RNA with magnetic nanoparticles could be a simple, quick and highly efficient method.

    Synthesis, Structure and Properties of Two New Coordination Polymers Based on 4-[(8-Hydroxy-5-quinolinyl)azo]-benzenesulfonic Acid
    LUO Yanan, XU Xianzhu, SUN Fuxing, YU Xiaoyang, ZHANG Xiao, ZHANG Ting, YU Liying
    2014, 30(1):  27-31.  doi:10.1007/s40242-013-3236-y
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    Two new coordination polymers based on 4-[(8-hydroxy-5-quinolinyl)azo]-benzenesulfonic acid(H2L), {[CdL(H2O)2]·H2O}n(1) and {[CdL(en)]·EtOH}n(2)(en=ethylenediamine), were solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Compounds 1 and 1 exhibit infinite 1D ladder-shaped chain structures, which are isostructural except that the two coordinating water molecules in compound 1 were replaced by one en molecule in compound 2 due to the use of different organic base. Compounds 1 and 2 were constructed into different supramolecular frameworks by hydrogen bonding and ππ stacking interactions. In addition, the fluorescent properties of compounds 1 and 2 were investigated. Furthermore, they were also investigated via IR spectral analysis, elemental analysis, powder X-ray diffraction(PXRD) and thermogravimetric analysis(TGA).

    Rhodamine 6G-based Chemosensor for the Visual Detection of Cu2+ and Fluorescent Detection of Hg2+ in Water
    HE Song, LIU Qiuchen, LI Yuanyuan, WEI Fangfang, CAI Songtao, LU Yan, ZENG Xianshun
    2014, 30(1):  32-36.  doi:10.1007/s40242-014-3364-z
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    A novel water soluble chemosensor 1 based on rhodamine 6G spirolactam scaffold has been synthesized and characterized. Upon addition of a wide range of the environmentally and biologically relevant metal ions, chemosensor 1 shows a colorimetric selective Cu2+ recognition from colorless to pink confirmed by UV-Vis absorption spectral changes, while it also exhibits a fluorometric selective Hg2+ recognition by fluorescence spectrometry. An absorption enhancement factor over 17-fold with 1-Cu2+ complex and a fluorescent enhancement factor over 45-fold with 1-Hg2+ complex were observed. Their recognition mechanisms were assumed to be a 1:1 stoichiometry for 1-Cu2+ complex and a 1:2 stoichiometry for 1-Hg2+ complex, respectively, which were proposed to be different ligation leading to the ring-opening of rhodamine 6G spirolactam. Furthermore, the detection limits for Cu2+ or Hg2+ were 3.3×10-8 or 1.7×10-7 mol/L, respectively.

    Extraction of Catechin Compounds from Green Tea with a New Green Solvent
    ZHANG Heng, TANG Baokun, ROW Kyungho
    2014, 30(1):  37-41.  doi:10.1007/s40242-014-3339-0
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    An emerging green solvent called a deep eutectic solvent(DES) was applied to the extraction and determination of catechin(C), (+)epicatechin gallate(ECG) and (-)epigallocatechin gallate(EGCG) from Chinese green tea. After evaluating different combinations of them by extraction methods and DESs, a DES-based extraction method was established and optimized by a systematic investigation of the influencing factors. As a result, a total of 3.629, 35.25 or 114.2 mg/g catechin, (+)epicatechin gallate or (-)epigallocatechin gallate were extracted respectively under optimal conditions with extraction efficiencies of 82.7%, 92.3% and 97.0%, respectively. By comparing with other common used solvents for extracting catechin compounds, DESs were proved to be potential extraction solvents for bioactive ingredients.

    Molecularly Imprinted Polymer Thin Film Based Surface Plasmon Resonance Sensor to Detect Hemoglobin
    WANG Yang, ZHANG Qingwen, REN Yamin, JING Lijing, WEI Tianxin
    2014, 30(1):  42-48.  doi:10.1007/s40242-013-3330-1
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    Molecularly imprinted polymer(MIP) films for hemoglobin detection were prepared onto the Au/Cr coated surface plasmon resonance(SPR) sensor chips by the in situ electropolymerization of 3-aminophenylboronic acid(3-APBA). The formation of the films and rebinding processes of hemoglobin were monitored by in situ electrochemical-SPR(EC-SPR) spectroscopy, with allowed real-time observation of the simultaneous changes in electrochemical and optical properties of the films. Scanning electron microscopy(SEM) and atomic force microscopy(AFM) were used to characterize the surface morphologies of the MIP films. The effects of pH, ion strength, different metal ions on rebinding Hb, the specific binding and the selective recognition were investigated. The results obtained with the molecular imprinted SPR chips indicate a good adsorption of Hb in a range of 0.0005―5 mg/mL in 0.05 mol/L sodium phosphate buffer at pH=7.0. A linear calibration curve(R2=0.94) of the SPR sensor for Hb detection was obtained in a range of 0.05―5 mg/mL. The detection limit for hemoglobin by this method was 0.000435 mg/mL(S/N=3). Interference studies indicate that the MIP films have a good selectivity compared with the referenced proteins. The stability of the sensor was also established. Results indicate that the SPR sensor chip keeps 87.6% of its original response after 14 d of storage under dry and ambient conditions.

    Synthesis and Antitumor Activity of 4-tert-Butyl-5-benzyl-2-benzyliminothiazoles
    YE Jiao, QIU Shenyi, HU Aixi, PENG Junmei, QIN Zhi
    2014, 30(1):  49-54.  doi:10.1007/s40242-013-3345-6
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    A series of novel Schiff bases including 4-tert-butyl-5-benzyl-2-benzyliminothiazoles was synthesized by reacting the aromatic aldehydes with the corresponding 2-aminothiazoles. The antitumor bioassay revealed that compounds 2n and 2m exhibited potent cytotoxicity against human cervix cancer(HeLa) cell line with IC50 values of 0.001 and 0.007 mmol/L, respectively. The preliminary structure-activity relationship(SAR) investigations and the apoptosis evaluation suggest that 4-tert-butyl-5-benzyl-2-benzyliminothiazoles may be a satisfactory backbone for antitumor activity, and compound 2n can serve as an attractive candidate for the development of novel apoptosis in anticancer treatment.

    Silica-supported Thionyl Chloride-assisted Synthesis and Bioassay of Novel Tetrazinan-3-thione and 3-Oxo-pyrazolidine-4-carbonitrile Derivatives of Steroids
    PARVEEN Mehtab, MALLA Ali Mohammed, ALI Akhtar, ALAM Mahboob, MUSTAFA Mir Faisal
    2014, 30(1):  55-62.  doi:10.1007/s40242-014-3308-7
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    A series of tetrazinan-3-thione and 3-oxo-pyrazolidine-4-carbonitrile derivatives of steroids(13) were synthesized with silica-chloride as a heterogeneous catalyst. The synthesized compounds 49 were obtained in substantial yields. In vitro evaluation of anticancer and antioxidant activity of the synthesized compounds was carried out via 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide(MTT) and 1,1-diphenyl-2-picrylhydrazyl(DPPH) assays, respectively. Compound 6 exhibited promising anti-proliferative activity towards a panel of cancer cell lines. The significant activity of compound 6 was further ascertained on structural, molecular modelling and docking studies. This study may provide a valuable insight into the further design and development of more potent biologically active compounds.

    Crystal Growth and Characterization of Fluorinated Perylene Diimides
    HUANG Jiachi, LI Hanying, MO Xiong, SHI Minmin, WANG Mang, CHEN Hongzheng
    2014, 30(1):  63-67.  doi:10.1007/s40242-013-3294-1
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    One-dimensional crystals of fluorinated perylene diimides were achieved by the self-assembly of them via solvent-nonsolvent exchanging. The π-conjugated fluorinated perylene diimides were assembled into highly-ordered nanostructures of well-defined morphologies in organic solvents due to the π-π interaction between the aromatic cores. It was found that with more introduced F atoms, perylene diimides showed remarkably improved solubility and thus were much easier to grow into crystals, due to the increased polarity induced by the strong electron-withdrawing F group. More importantly, single crystal of N,N'-diperfluorophenyl-3,4,9,10-perylenetetracarboxylic diimide(DPFPP) was obtained, and the unit cell-dimensions of triclinic structure were determined by the selected area electron diffraction(SAED) patterns to be a=0.712 nm, b=1.072 nm, c=2.914 nm, α=97.0°, β=89.6°, γ=93.4°. Owing to most of the longest c-axis orienting nearly vertically to the long axis of the needle crystal, the molecular planes are expected to be vertical to the needle axis.

    Environmentally Benign Synthesis of 2-Pyrazolines and Cyclohexenones Incorporating Naphthalene Moiety and Their Antimicrobial Evaluation
    Al-Bogami Abdullah Saad
    2014, 30(1):  68-74.  doi:10.1007/s40242-013-3290-5
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    We reported the environmental benign synthesis of chalcones, 2-pyrazolines and cyclohexanones under microwave irradiation. Chalcones were obtained by the condensation of each of 2-hydroxyacetophenone derivatives with α-naphthaldehyde under microwave irradiation. The condensation reactions of each of synthesized chalcones with phenyl hydrazine under microwave irradiation in the presence of dry acetic acid as a cyclizing agent gave 2-pyrazolines. Also, the new cyclohexenone derivatives, valuable intermediates to synthesize fused heterocycles, have been prepared by the cyclocondensation of each of hydroxychalcones with ethyl acetoacetate. The structures of the synthesized compounds were elucidated by infrared(IR) spectrometry, nuclear magnetic resonance(NMR), mass spectrometry(MS) and elmental analysis. The results indicate that unlike classical heating, microwave irradiation results in higher yields with shorter and cleaner reactions. The synthesized compounds were screened for antimicrobial activity against Staphylococcus aureus, Escherichia coli, Candida Albicans and Aspergillus niger. We clarified the effects of different substituents in the tested compounds on the obtaind antibacterial activities and antifungal activities .

    Synthesis and Antitumor Activities of Novel 4-Morpholinothieno[3,2-d]pyrimidine Derivatives
    SONG Kaizhen, MA Junjie, WANG Xiao, GONG Ping, ZHAO Yanfang
    2014, 30(1):  75-81.  doi:10.1007/s40242-013-3281-6
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    A series of novel 2-hydrazinyl-4-morpholinothieno[3,2-d]pyrimidine derivatives was designed and synthesized. All of them were screened for their cytotoxic activities against large cell lung cancer(H460), colon cancer (HT-29) and adenocarcinomic lung cancer(A549) cell lines in vitro. The pharmacological results indicate that most of the target compounds show moderate to significant activities. Especially compound 17 exhibits the most potent antitumor activities against H460, HT-29 and A549 cell lines with IC50 values of 0.57, 0.45 and 1.45 μmol/L, respectively.

    Synthesis and Herbicidal Activities of 2-Methylpropan-2-aminium O-Methyl 1-(Substituted Phenoxyacetoxy)alkylphosphonates
    PENG Hao, DENG Xiaoyan, GAO Ling, TAN Xiaosong, HE Hongwu
    2014, 30(1):  82-86.  doi:10.1007/s40242-014-3203-2
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    A series of 2-methylpropan-2-aminium O-methyl 1-(substituted phenoxyacetoxy)alkylphosphonates (5a―5o) was selectively synthesized by reacting the corresponding O,O-dimethyl 1-(substituted phenoxyacetoxy)-alkylphosphonates with an excess of 2-methylpropan-2-amine. The results of preliminary bioassays show that the title compounds exhibit moderate to good herbicidal activities against Brassica napus and Echinochloa crusgalli. Furthermore, compounds 5a―5j, which show much higher activities than compounds 5k―5o, were selected to further evaluate their post-emergence herbicidal activity at a dosage of 150 g/ha(1 ha=10000 m2). Especially, 2-methylpropan-2-aminium O-methyl 1-[2-(4-chloro-2-methylphenoxy)acetoxy]butylphosphonate(5h) shows 100% inhibitory effect on the growth of Brassica juncea and Amaranthus retroflexus, which is comparable with the commercial herbicide 2,4-dichlorophenoxy acetic acid(2,4-D).

    Zinc Complexes Supported by N, N-Dimethylaniline-arylamido Ligands:Synthesis, Characterization and Catalytic Properties for Ring-opening Polymerization of L-Lactide
    YAO Wei, XUE Yingzhao, LIU Tiantian, GAO Aihong, WANG Yanfeng
    2014, 30(1):  87-90.  doi:10.1007/s40242-014-3183-2
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    The reaction of bidentate N,N-dimethylaniline-arylamido ligands, o-C6H4NMe2(CH2NHAr)(Ar = Ph, 1a; 2,6-Me2C6H3, 1b; 2,6-Et2C6H3, 1c; 2,6-iPr2C6H3, 1d) with ZnEt2 yields the complexes o-C6H4(NMe2)(CH2NAr)ZnEt (2a—2d), respectively. All the complexes were characterized by 1H and 13C NMR spectroscopy and elemental analyses. It was found that all the zinc complexes were efficient catalysts for the ring-opening polymerization of L-lactide in the presence of benzyl alcohol with good molecular weight control and narrow polydispersity.

    Biological Evaluation and Structure Modification of (S)-3-Aminopyrrolidine Derivatives
    XIN Tian, ZHANG Cunlong, TAN Chunyan, JIANG Yuyang
    2014, 30(1):  91-97.  doi:10.1007/s40242-014-3174-3
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    With our interest in (S)-3-aminopyrrolidine derivatives, we further screened inhibition activities of three hit compounds on many other kinases with the results demonstrating that this series of compounds shows better anticancer activities, which might result from the main block of PI3K/Akt signaling pathway and the inhibition of Abelson murine leukemia viral oncogene homolog(ABL) kinase, as well as some epidermal growth factors. Further structure modification demonstrates that benzylsulfonyl group is the necessary functional group contributing to the biological activity that will be helpful to guiding us to optimize these (S)-3-aminopyrrolidine derivatives.

    Synthesis and Biological Activities of Novel Methyl Xanthine Derivatives
    CHEN Youwei, WANG Baolei, GUO Yanjun, ZHOU Yunyun, PAN Li, XIONG Lixia, YU Shujing, LI Zhengming
    2014, 30(1):  98-102.  doi:10.1007/s40242-014-3173-4
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    Caffeine is one of methyl xanthine compounds, which has the similar mode of action as ryanodine receptor insecticide. In order to find novel and efficient insecticide, structural modification of certain methyl xanthine compounds was made by introducing some common pesticidal active moieties into the structure of caffeine. Eleven novel methyl xanthine compounds were synthesized and characterized by 1H nuclear magnetic resonance(1H NMR), elemental analylsis or high-resolution mass spectrometry(HRMS). According to the biological activity results, it was found that these new compounds show moderate activity towards Mythimna separata Walker and Culex pipiens pallens. For example, compound 2d shows a lethality rate of 40% at 200 mg/L towards Mythimna separata Walker, compounds 2i and 2f show 56.7% and 53.3% lethality rates at 2 mg/L towards Culex pipiens pallens, which are all better than caffeine. In addition, some compounds of them show moderate antifungal activity to some plant pathogenous fungi.

    Novel Chemical Strategy for the Synthesis of RGDCySS Tetrapeptide
    XU Baofeng, YANG Sen, ZHU Jinming, MA Yudan, ZHAO Gang, GUO Yi, XU Li
    2014, 30(1):  103-107.  doi:10.1007/s40242-014-3228-6
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    A new route was described to synthesize Arg-Gly-Asp-X(RGDX, X=amino acid) tetrapeptide. To better understand the method, the tetrapeptide Arg-Gly-Asp-CySS(RGDCySS) was chosen as a model target for X. First, GDCySS was obtained in four steps, comprising the chloroacetylation of L-aspartic acid(ClCH2COAsp), synthesis of chloroacetyl L-aspartic acid anhydride[ClCH2COAsp(CO)2O], formation of ClCH2COAsp-CySS and ammonolysis of ClCH2COAsp-CySS. Second, preparation of Arg-NCA, which was coupled with GDCySS to synthesize RGDCySS by the NCA method(Leuchs' anhydrides method, NCA: N-carboxy-α-amino acid anhydride). The purity of the product was analyzed by the high performance liquid chromatography(HPLC). Molecular weights of the peptide products were confirmed by mass spectroscopy. In the developed approach, less protected amino acids were used compared to conventional solid-phase synthesis. The new route offers advantages of low cost, simplicity and rapid synthesis with a reasonable yield of 63.0%(calculated according to arginine content).

    Apoptosis of T-47D Cells Induced by Cinobufacini via a Caspase-3-dependent Manner
    WANG Weiqi, SHI Aiping, FAN Zhimin
    2014, 30(1):  108-113.  doi:10.1007/s40242-014-3196-x
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    To investigate the mechanism of the anti-tumor activity of cinobufacini on the breast cancer cell line T-47D, the inhibitory effect of cinobufacini on the proliferation of T-47D was detected via MTT assay and the morphological changes of T-47D and HBL-100 cells caused by cinobufacini were observed with an inverted microscope. Cell apoptosis and cell cycle stages were detected by flow cytometry analysis. The effects of cinobufacini on the expression of active-form and pro-form of caspase-3 were assessed by Western blot analysis. Cinobufacini dramatically inhibited T-47D proliferation in a dose-and time-dependent manner. We found that more than 20% of T-47D cells were killed after treatment with 20 mg/mL cinobufacini for 24 h in vitro. After 6 d of treatment with 20 mg/mL cinobufacini, the cell survival rate decreased by more than 40%. Flow cytometric analysis demonstrated that cinobufacini induced significant apoptosis and changes of the cell cycle distribution of T-47D cells. We used breast cell line HBL-100 as the control, the above experiments except cell cycle analysis showed that cinobufacini more obviously induced the apoptosis of T-47D cells than that of HBL-100 cells. Western blot analysis confirmed the protein expression of active caspase-3 increased with increasing the dose of cinobufacini. These results indicate that cinobufacini induces the apoptosis of T-47D cells via the up-regulation of caspase-3.

    Selective 3,4-Polymerization Mechanism of Isoprene Catalyzed by Rare Earth Alkyl Complexes
    LIU Ying, SUN Cuihong, LI Xiaofang, ZHANG Shaowen
    2014, 30(1):  114-118.  doi:10.1007/s40242-014-3483-6
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    The mechanism of selective 3,4-polymerization reaction of isoprene catalyzed by the rare earth lutecium(Ⅲ) alkyl complexes [2,6-Me2Ph―N―CH2―C(CH2SiMe3)=N―PhMe2-2,6]Lu(CH2SiMe3)2(THF) was investigated by means of the M06/sdd method with solvation effects taken into account. The results show that the structure of the catalyst core remained almost unchanged as the isoprene molecules were alternatively inserted into the complex at two opposite sides. The Gibbs free energies of the coordination complexes, transition state and intermediates indicate that all the isoprene molecules prefer to insert into the complex with the 3,4-polymerization selectivity as catalyzed by the catalyst, which is consistent with the experimental observations. It is found that the insertion reaction of each isoprene is exothermic, which comes mainly from the coordination of the isoprene molecule to the lutecium(Ⅲ) atom. The solvation effects were confirmed important in predicting the Gibbs free energies of the present reaction system.

    Synthesis, Characterization and Thermophysical Properties of Three Neoteric Solvents-Ionic Liquids Based on Choline Chloride
    POPESCU Ana-Maria, CONSTANTIN Virgil
    2014, 30(1):  119-124.  doi:10.1007/s40242-014-3346-1
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    The authors prepared, characterized and preliminary studied the properties of some neoteric solvents-ionic liquids based on choline chloride, i.e., three ionic liquids based on the eutectics of choline chloride(2-hydroxy-N,N,N-trimethylethanaminium chloride) with, respectively, urea, malonic acid and citric acid. The obtained mixtures were clear and colorless ionic liquids at room temperature. The thermophysical properties, namely, density, viscosity, and electrical conductivity of these mixtures were investigated as a function of temperature within a range of 298—353 K. Correlations for the temperature dependence of the measured properties were generated and discussed in terms of Arrhenius theory. Finally the electrochemical windows of the eutectic liquids were determined.

    Theoretical Studies on Complexes of Calcium Ion with Amino Acids
    QIN Penghua, LÜ Wencai, QIN Wei, ZHANG Wei, XIE Hui
    2014, 30(1):  125-129.  doi:10.1007/s40242-014-3303-z
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    The complexes formed by calcium ion and 12 common amino acids were investigated systematically in the gas phase at the level of MP2/6-311++G(d,p)//MP2/6-31G(d,p). The results show that the salt-bridge structure is the most preferred motif for Ca2+ binding aliphatic amino acids without heteroatom in the side chain, while charge-solvated(CS) structure is the most preferred motif for Ca2+ binding other amino acids except for glutamine and lysine. IR spectra of Gln-Ca2+ and Asn-Ca2+ complexes were calculated and compared well with the available experiments. From the study in aqueous solution, the bidentate salt-bridge structure was determined to be the most favo-rable for all the twenty kinds of amino acids to chelate Ca2+ to both the oxygen atoms of the negatively carboxylate group in the backbone.

    Thermal Kinetics and Decomposition Mechanism of 1-Amino-1, 2, 3-triazolium Nitrate
    DU Xujie, LI Xiaodong, YANG Rongjie, LI Yuchuan, PANG Siping
    2014, 30(1):  130-136.  doi:10.1007/s40242-014-3299-4
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    The thermal decomposition kinetics of 1-amino-1,2,3-triazolium nitrate(ATZ-NO3) was investigated by non-isothermal TG-DTG at various heating rates(2, 5, 10, 15 and 20 ℃/min). The results show that the thermal decomposition of ATZ-NO3 consists of two stages corresponding to the losing of nitrate anion, substituent group and the splitting of triazole ring respectively. The kinetic triplets of the two stages were described by a three-step method. First, the differential Kissinger and intergral Ozawa methods were used to calculate the apparent activation energies(E) and pre-exponential factors(A) of the two decomposition stages. Second, two calculation methods(intergral Šatava-Šesták and differential Achar methods) were used to obtain several probable decomposition mechanism functions. Third, three judgment methods(average, double-extrapolation and Popescu methods) were used to confirm the most probable decomposition mechanism functions. Both reaction models of the two stages were random-into-nucleation and random-growth mechanisms with n=3/2 for the first stage and n=1/3, m=3 for the second stage. The kinetic equations for the two decomposition stages of ATZ-NO3 may be expressed as da/dt=1013.60·e-(RT/128970)(1-a)[-ln(1-a)]-(2/3) and da/dt=1011.41·e-(RT/117370)(1-a)[-ln(1-a)]-(1/2). The thermodynamic parameters including Gibbs free energy of activation(ΔG), entropy of activation(ΔS) and enthalpy of activation(ΔH), for the thermal decomposition reaction were also derived.

    Synthesis and Release Behavior of a Hybrid of Camptothecin Intercalated Dodecyl Sulfate Modified Layered Double Hydroxide
    LI Yan, DU Na, HOU Wanguo, LIU Shaojie
    2014, 30(1):  137-143.  doi:10.1007/s40242-014-3284-y
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    The intercalation of a non-ionic and poorly water-soluble drug, camptothecin(CPT), into dodecyl sulfate (DS) modified layered double hydroxide(LDH) was carried out via a secondary intercalation method to obtain a CPT-DS-LDH hybrid. The in vitro CPT release eFxaminations from the hybrid show that the hybrid can well control the release of CPT, which indicates that the hybrid is a potential drug controlled-release system. Moreover, the intercalation kinetics of CPT into the DS modified LDH fits for the pseudo-second-order model. And the release kinetic process of CPT from the CPT-DS-LDH hybrid at pH=4.8 can be described with pseudo-first-order model, while that at pH=7.2 can be described with both pseudo-first-order model and pseudo-second-order model. Meanwhile, the release mechanism of CPT from the CPT-DS-LDH hybrid was discussed.

    Evaporation-induced Morphology Pattern of Triblock Copolymer A5B10C5 in Thin Film:a Multibody DPD Simulation Study
    LI Yang, WANG Dequan, WANG Wei, LI Yanchun, HUANG Xuri, SUN Chiachung, JIN Mingxing
    2014, 30(1):  144-148.  doi:10.1007/s40242-013-3260-y
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    We used multibody dissipative particle dynamics method, by which the attractive and repulsive interactions can be effectively considered, to investigate the evaporation-induced morphology patterns of triblock copolymer A5B10C5 in thin film. With changing attractive interactions between solvent vapor and triblock copolymer that represent various selective solvents, lamellar morphology, sandwich lamellar morphology, spherical morphology and disorder morphology patterns of the thin films were obtained for both coil-coil-coil and rod-coil-coil chain architectures, respectively. The order parameter and the film thickness were calculated during the process for characterizing the film properties, and it was found that the rigid A-block of the triblock copolymer hinders the formation of an ordered structure.

    Effects of Experimental Conditions and Kinetics of Photodegradation of Methylene Blue over TiO2
    WIDCHAYA Radchatawedchakoon, ARAYA Thapol, RATCHANEEKORN Wanchanthuek
    2014, 30(1):  149-156.  doi:10.1007/s40242-013-3177-5
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    The authors investigated the catalytic activity of TiO2 for methylene blue(MB) degradation under solar light. The reaction parameters such as reaction time, TiO2 content, temperature, pH, MB concentration and light irradiation were in attention. Then, the experimental data was analyzed to investigate the adsorption order and adsorption model. The results indicate that the optimum conditions for the removal of MB are a TiO2 content of 0.5 g/L, 0.50 mg/L MB solution, a temperature of 30 ℃ and reaction time of 60 min. It was found that the amount of MB removal was decreased when the pH and temperature increased. This suggests that the removal process is exothermic. However, the solar light irradiation plays a vital role in enhancing the removal amount of MB. In the dark reaction, the ability of TiO2 to remove MB was increased when the pH increased. The kinetics studies confirm that the adsorption of MB is the Pseudo-second-order. And the adsorption model was fitted with the Freundlich isotherm.

    Label-free Detection of Biotin Using Nanoporous TiO2/DNA Thin-film Coated Wavelength Interrogated Surface Plasmon Resonance Sensors
    LI Qiushun, HE Hao, WANG Junnan, ZHENG Hui, SHI Jianguo, LI Mingyu, DONG Wenfei, QI Zhimei
    2014, 30(1):  157-162.  doi:10.1007/s40242-014-3312-y
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    The sensing sensitivity of the wavelength interrogated surface plasmon resonance(WISPR) biosensor could be improved by self-assembly of nanoporous thin-film of TiO2 nanoparticles/DNA(TiO2/DNA)n(n is the number of bilayer) on wavelength interrogated surface plasmon resonance(WISPR) chips. The growth behavior and surface structure of the nanoporous thin-film were investigated by UV-Vis spectroscopy and scanning electron microscopy, respectively. The home-made WISPR sensor with Krestchmann configuration consisted of a tungsten-halogen lamp as a photon source and a CCD camera as the detector. After the deposition of (DNA/TiO2)n thin film on WISPR chips, the resonance peak of the reflection spectra appeared in air. With the increases of n, the resonance wavelength gradually red shifted, which is consistent with the simulated results. After the optimization of the porous film, the WISPR biosensor was utilized to detect low-molecular-weight analytes, such as biotin. The result demonstrates that the sensitivity of [poly(styrene sulfonate)/polyally lamine hydrochlorides]5(PSS/PAH)5 could be 4 times higher than that of polyelectrolyte multilayer modified WISPR sensor.

    Effect of Draw Ratio on the Morphologies and Properties of BPDA/PMDA/ODA Polyimide Fibers
    ZHANG Chunling, ZHANG Qiong, XUE Yanhu, LI Guomin, LIU Fangfang, QIU Xuepeng, JI Xiangling, GAO Lianxun
    2014, 30(1):  163-167.  doi:10.1007/s40242-014-3266-0
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    3,3,4,4-Biphenyltetracarboxylic dianhydride/pyromellitic dianhydride/4,4-oxydianiline(BPDA/PMDA/ ODA) polyimide copolymer fibers with different draw ratios were prepared from the imidization of polyacrylic acid(PAA) fibers via a dry-jet wet-spinning process. Their morphologies, microcrystal orientations, thermal stabilities, and mechanical properties were investigated via scanning electron microscopy(SEM), wide angle X-ray diffraction(WAXD), thermogravimetric analysis(TGA), and tensile experiments. In order to acquire fibers with better mechanical performance, we aimed at obtaining the optimal draw ratio. Drawing during thermal imidization resulted in a decreased diameter of fiber from 25.8 μm to 16.9 μm corresponding to draw ratio from 1 to 3.5. WAXD results show that the degree of the orientation of the undrawn sample is 64.1%, whereas that of the drawn sample is up to 82%. The as-spun fiber and those with different draw ratios all exhibit high thermal stabilities, i.e., the temperature at a mass loss of 5% can reach as high as 570 ℃. The tensile strengths and tensile modulus of the fibers increase with the draw ratios, and the maximum tensile strength and modulus are 0.90 and 12.61 GPa, respectively.

    Synthesis and Characterization of Biodegradable Alternating Polyesteramides from Mixed Diamidediols and Sebacic Acid
    SUN Huiyun, YIN Tiao, LI Yue, ZHAO Jingbo, ZHANG Zhiyuan, ZHANG Junying
    2014, 30(1):  168-175.  doi:10.1007/s40242-014-3189-9
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    A series of polyesteramide prepolymers[PrePEA(0/4,8)s] having mixed alternating bisesterdiamide units was synthesized via melt polycondensation from N,N'-bis(2-hydroxyethyl)oxamide(0) and N,N'-bis(2-hydroxyethyl)-adipamide(4) with sebacic acid(8) at different molar ratios. Chain extension of them was conducted with 2,2'-(1,4-phenylene)-bis(2-oxazoline) and adipoyl biscaprolactamate as combined chain extenders. The chain extended polyesteramides[ExtPEA(0/4,8)s] were characterized by proton nuclear magnetic resonance(1H NMR), gel permeation chromatography(GPC), differential scanning calorimetry(DSC), thermogravimetry analysis(TGA), wide angle X-ray scattering, tensile test and enzymatic degradation. The results show that ExtPEA(0/4,8)s were crystalline polyesteramides. They had Tm up to 136.5 ℃ and initial decomposition temperature above 297.5 ℃. They crystallized in similar crystallites into Nylon-66 and degraded under the catalysis of protease or lipase. They are thermoplastic materials with tensile strength up to 21.5 MPa and elongation at break above 64.0%.

    Hydrothermal Synthesis of PEG-capped ZnS:Mn2+ Quantum Dots Nanocomposites
    ZHANG Yinan, JIANG Dong, HE Zhi, YU Yunwu, ZHANG Haibo, JIANG Zhenhua
    2014, 30(1):  176-180.  doi:10.1007/s40242-013-3101-z
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    Water-soluble Mn2+-doped ZnS nanocrystals surface capped with polyethylene glycol(expressed as PEG-ZnS:Mn2+) were synthesized in aqueous solution with PEG as surface modifier without ligand exchange. The particles were obtained via chemical precipitation method at 100 ℃ with an average diameter of 3 nm and a zinc blende structure. The PEG modified on the surface of PEG-ZnS:Mn2+ nanocrystals rendered the nanocrystals water soluble and biocompatible. And the PEG-ZnS:Mn2+ nanocrystals have the potential application in molecular assembly and biological fluorescence analysis. The effects of the Mn2+ concentration, stabilizer concentration, and synthesis time on the photoluminescence(PL) intensity of ZnS:Mn2+ QDs were also investigated.

Editor-in-Chief:
Jihong YU
ISSN 1005-9040
CN 22-1183/O6
Special Issue/Column
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