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01 December 2013, Volume 29 Issue 6

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Cover and Content of Chemical Research in Chinese Universities Vol.29 No.6(2013)

2013, 29(6):  0-0. 

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Grafting β-CD Copolymer Metal Complex from Silicon Gel by SI-ATRP

JIANG Yan, LIANG Yuan, ZHANG Hong-wen, ZHANG Rong

2013, 29(6):  1029-1031.  doi:10.1007/s40242-013-3322-1

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Articles

Fabrication and Visible Light Photocatalytic Activity of Co-doped ZnO Nanorods

LI Xue, LI Jin-hua, LI Shi-jun, FANG Xuan, FANG Fang, CHU Xue-ying, WANG Xiao-hua, HU Jia-xin

2013, 29(6):  1032-1035.  doi:10.1007/s40242-013-3354-6

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Co-doped ZnO nanorods were prepared by electrochemical deposition method in aqueous solution. To study the as-grown samples, several characterizations were carried out. The scanning electron microscopy(SEM) images show that the samples present a rod-like shape with hexagonal cross sections and roughened surface. There is a slight shift for (002) diffraction peak of Co-doped ZnO nanorods in XRD because Co²⁺ ions entered into the ZnO lattice. Energy-dispersive X-ray spectroscopy(EDS) and X-ray photoelectron spectroscopy(XPS) results also show the exist of Co in the sample. Photoluminescence(PL) spectra of the samples were observed at room temperature, the UV emission of Co-doped ZnO shows a slight red shift compared with that of undoped ZnO. Thus, we can reach the conclusion that Zn²⁺ ions have been substituted by Co²⁺ ions in the ZnO samples. In addition, photocatalysis property of Co-doped ZnO nanorods was investigated under the irradiation of visible light. It was found that the degradation rate of methyl orange is increased greatly by Co-doped ZnO nanorods in comparison to undoped ZnO nanorods.



Synthesis and Characterization of TS-1 with Aid of Supercritical CO₂

ZHU Guo-wei, CHEN Xiao-bo, JIANG Hong, HUANG Jian, WANG Run-wei, QIU Shi-lun

2013, 29(6):  1036-1039.  doi:10.1007/s40242-013-3248-7

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A new route to synthesize TS-1 has been developed using the supercritical carbon dioxide(SCCO₂) as a crystallization-assistant agent. SCCO₂ plays a dual role: as a reagent changing the alkalinity during the crystallization process and as a medium eliminating mass-transfer limitations(both within the bulk fluid and through liquid/gas, solid/gas or solid/liquid phase boundaries). In this route, it was shown that the Ti content in TS-1 increase compared with that in the TS-1 prepared without SCCO₂, but decrease while the SCCO₂ pressure increase. The prepared crystal morphology also underwent significant change. The crystallization time of TS-1 can be shorten a lot.



Facile Solution-based Synthesis and Optical Properties of Co₃O₄ Nanoparticles at Low-temperature

LI Yun-ling, ZHAO Jing-zhe, ZHAO Yan, HAO Xin-li, HOU Zhen-yu

2013, 29(6):  1040-1044.  doi:10.1007/s40242-013-3137-0

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Cobalt oxide(Co₃O₄) with different morphologies was achieved by a simple solution-based method. Various parallel experiments show that several experimental parameters, such as the concentrations of NaOH and ethylene glycol(EG), play important roles in the morphological controlling of Co₃O₄ nanoparticles. A lower concentration of NaOH favors quasi-spherical product with a uniform size of about 15 nm, whereas a higher concentration of NaOH generally leads to the formation of nanoplates with wide size distribution. In addition, Co₃O₄ nanorods were also obtained partially by introducing a certain amount of EG. A possible mechanism was proposed for the selective formation of Co₃O₄ with various morphologies. X-Ray diffraction(XRD), infrared(IR) spectrometry, scanning electron microscopy(SEM), transmission electron microscopy(TEM) and UV-Vis spectrometry were used to characterize the samples.



Synthesis, Structure and Fluorescent Property of Coordination Polymer from 4-[(8-Hydroxy-5-quinolinyl)azo]-benzoic Acid

LUO Ya-nan, XU Xian-zhu, ZHANG Xiao, YU Xiao-yang, QU Xiao-shu, YANG Yan-yan, SHEN Qi-hui

2013, 29(6):  1045-1049.  doi:10.1007/s40242-013-3100-0

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One new coordination polymer based on 4-[(8-hydroxy-5-quinolinyl)azo]-benzoic acid(H₂L), {[CdL(H₂O)]·H₂O}_n(1) was solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction, infrared spectrometry, elemental analysis, powder X-ray diffraction(PXRD) and thermogravimetric analysis (TGA). In compound 1, L^2- ligands link Cd(Ⅱ) to form a sinusoidal ruffling layer, in which the carboxylic groups connect Cd(Ⅱ) into an infinite Cd―O chain. And the layers are further stabilized by hydrogen bonding and π…π interactions, forming a three-dimensional(3D) supramolecular network. In addition, the fluorescent property of compound 1 was also investigated.



High-temperature High-pressure Hydrothermal Synthesis of Dy³⁺-doped YNbO₄ Single Crystal and Its Luminescence Properties

YANG Min, LI Qi-liang, WANG Ying, LIU Xiao-yang, WANG Xiao-feng

2013, 29(6):  1050-1054.  doi:10.1007/s40242-013-3086-7

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Single crystal Dy³⁺ doped YNbO₄ phosphors were prepared via a high-temperature high-pressure hydrothermal procedure. Under excitation at 270 nm, the Dy³⁺-doped YNbO₄ phosphor shows bright white emission, which is composed of two strong bands at 492 and 576 nm corresponding to the characteristic ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transitions of Dy³⁺, respectively. The dominant band was observed at 352 nm, which corresponds to the ⁶H_15/2→⁶P_7/2 transition of Dy³⁺. Nearly white light was achieved at λ_ex 270, 310 and 388 nm and the CIE(International Commission on Illumination) values were (0.3135, 0.3421), (0.3088, 0.3380) and (0.3146, 0.3296), respectively.



Volume-related Efficiency of Gadolinium Polyoxometalates as MRI Contrast Agents

KONG Da-liang, WEI Bo, ZHOU Sheng-yan, YANG Hai-shan, JIANG Yang

2013, 29(6):  1055-1058.  doi:10.1007/s40242-013-3061-3

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Two gadolinium polyoxometalates, KCs₄[Gd(α-SiW₁₁O₃₉)]·25H₂O(POM-1) and K₁₃[Gd(β₂-SiW₁₁O₃₉)₂]· 27H₂O(POM-2), have been evaluated as the candidates of potential magnetic resonance imaging T₁(longitudinal relaxation) contrast agents. Longitudinal relaxivities of POM-2 are much higher than those of POM-1 in pure water and protein solution, respectively. However, compared with POM-1, POM-2 interacts with protein more strongly through electrostatic interaction, which is comfirmed by the fluoresence quenching of human serum albumin(HSA) in solutions with different polyoxometalate concentrations. Meanwhile, POM-1 presentes much lower cytotoxicity in the cell viability tests.



Quantitative Analysis of Catalpol in Chinese Patent Medicine Lixin Pill by Near-infrared Diffuse Reflectance Spectroscopy

ZHANG Wei, BAI Xue-yuan, WANG Ying-ping, QU Zheng-yi, SUN Li-xia, YAO Chun-lin, ZHAO Bing

2013, 29(6):  1059-1062.  doi:10.1007/s40242-013-3231-3

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Lixin pill is a typical Chinese patent medicine with anti-rheumatic heart disease activity that has been widely used in clinical practice. Therefore it is very important to detect the concentration of catalpol, as the main component of the active ingredient. Near-infrared reflectance(NIR) spectroscopy was used to study the content of catalpol in the unprocessed Chinese patent medicine of Lixin pills. NIR is applied to quantitatively analyze 77 samples, which were randomly divided into a calibration set containing 61 samples and a prediction set containing 16 samples. To get a satisfying result, partial least squares(PLS) regression was utilized to establish quantitative models. In PLS regression, the values of coefficient of determination(R²) and root mean square error of cross-validation (RMSECV) of PLS regression are 0.9419 and 0.0216, respectively. The process of establishing model, parameters of model, and prediction results were also discussed in detail(root mean square error of prediction is 0.0164). The overall results show that NIR spectroscopy can be efficiently utilized for the rapid and accurate analysis of routine chemical compositions in the Chinese patent medicine of Lixin pills. The prediction set suggests that this quantitative analysis model has excellent generalization ability and prediction precision. Accordingly, the result can provide technical support for the further analysis of catalpol in unprocessed Lixin pill. Moreover, this study supplied technical support for the further analysis of other Chinese patent medicine samples.



Effects of Protein on the Detection of Chlorobenzenes in Fish and Their Elimination by Modified QuEChERS Method

DENG Qiao-qiao, LI Gui-zhi, LIU Pei-pei, ZHANG Xing-mei, LIU Yong-ming

2013, 29(6):  1063-1067.  doi:10.1007/s40242-013-3230-4

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Molecular fluorescence spectrometry, resonance Rayleigh scattering and gas chromatography-mass spectroscopy(GC-MS) were used to study the effect of pure fish serum albumin(FSA) as the model protein on the extraction of three chlorobenzenes(CBs: 1,3-DCB, 1,2-DCB and 1,2,4-TCB; DCB=dichlorobenzene; TCB=trichloroben-zene) in fish samples. The results show that there was a strong binding effect between CB and FSA. In an aqueous solution of 90%(volume fraction) acetone, a slow but full protein denaturation might take place, which would cause the unfolding of protein and the releasing of CBs. Based on these results, a QuEChERS(quick, easy, cheap, effective, rugged and safe) method was modified by replacing the traditional acetonitrile with acetone aqueous solution in the present work. This modified QuEChERS method was applied in the determination of CBs in fish samples. The spiked recoveries and the limits of detection were 80.4%―118.3% and 2.4―7.3 ng/g, respectively. This paper proposes a new strategy by slowing down the protein denaturation and releasing bound organic compounds to enhance the extraction efficiency of CBs in fish samples.



Antitumor Compound Identification from Zanthoxylum bungeanum Essential Oil Based on Composition-activity Relationship

LI Zi-dan, HAN Sheng-nan, JIANG Jian-lan, ZHANG Xiao-hang, LI Yan, CHEN Hao, YUAN Ying-jin

2013, 29(6):  1068-1071.  doi:10.1007/s40242-013-3223-3

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The chemical composition of Zanthoxylum bungeanum(Z. bungeanum) essential oil(39 batches) was analyzed by gas chromatography-mass spectrometry(GC-MS) analysis(23 ingredients), and the antitumor activity against HeLa cells was detected via the MTT[3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide] assay. Two composition-activity relationship(CAR) models, generalized regression neural network(GRNN) and support vector regression(SVR) were respectively used to calculate the mean impact value(MIV) so as to identify bioactive compounds. Among them 9 ingredients(peaks 4, 15, 7, 8, 13, 3, 16, 9 and 11) were selected due to their high absolute MIVs. All of them have been confirmed with potential antitumor activity by previous researches. The CAR model combined with MIV was expected to be a credible tool for the active compound identification from herbs.



Ultrasound-assisted Extraction of Kamebakaurin from Rabdosia excisa by Response Surface Methodology

TANG Jian, MA Rui-li, LI Qian-qian, JIANG Chun-bao, CHEN Rui, OUYANG Zhen, CHEN Hai-sheng, WANG Min

2013, 29(6):  1072-1077.  doi:10.1007/s40242-013-3169-5

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For the efficient extraction of kamebakaurin(KA), the ultrasound-assisted extraction(UAE) of KA from Rabdosia excisa(R. excisa) via response surface methodology(RSM) was investigated with high-performance liquid chromatography(HPLC). Effects of the experimental parameters such as extraction solvent, ratio of liquid to plant material, extraction time and extraction temperature on the extracting efficiency of KA from R. excisa were evaluated, and the purity of KA in residual was calculated. The optimized conditions were 65.5%(volume fraction) acetone, 35℃, time of 24.6 min with ultrasound of 80 W/L, 40 kHz, ratio of liquid to plant material at 30:1(mL/g). The maximum yield of KA is 0.708 mg/kg, with mean purity of 6.09%, indicating that ultrasound-assisted extraction is a feasible and useful method for extracting KA from R. excisa.



Rapid Quantification of Astilbin in Rat Plasma by Liquid Chromatography-tandem Mass Spectrometry and Its Application to Pharmacokinetic Study

YIN Lei, ZHANG Yun-hui, ZHAO Sen, CHENG Long-mei, SHI Mei-yun, YANG Yan, SUN Yan-tong, LIU Xi-dong, FAWCETT J. Paul

2013, 29(6):  1078-1082.  doi:10.1007/s40242-013-3166-8

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Astilbin is a potential immunosuppressive agent with minor cytotoxicity. Its oral bioavailability is supposed to be rather low and therefore a sensitive analytical method is required for its pharmacokinetic study after oral administration. A simple, sensitive and rapid liquid chromatography-tandem mass spectrometry(LC-MS/MS) method was developed and validated for the determination of astilbin in rat plasma. Plasma samples were subjected to liquid-liquid extraction with ethyl acetate and separated by reversed phase high performance liquid chromatography(HPLC) with methanol-0.01%(volume fraction) formic acid(50:50, volume ratio) as mobile phase. Quantitive determination was achieved on negative LC-MS/MS by a multiple reaction moitoring method with transitions m/z 449.1→150.9(quantifier) and m/z 449.1→284.9(qualifier) for astilbin and m/z 128.9→42.0 for internal standard(IS). A lower limit of quantification(LLOQ) of ng/mL was achieved within a short cycle time of 3.4 min. The method was successfully applied to a pharmacokinetic study involving oral and intravenous administrations of 6 mg/kg astilbin to six rats.



Synthesis and Optoelectronic Properties of Donor-acceptor Molecules Containing Pyromellitic Diimide Chromophore

ZHANG Qian, LU Xue-feng, WANG Zhong-sheng, ZHOU Gang

2013, 29(6):  1083-1088.  doi:10.1007/s40242-013-3225-1

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Three donor-acceptor molecules containing pyromellitic diimide chromophore were designed and synthesized. The synthetic route towards the target compounds was systematically investigated and discussed in detail. The resulted organic semiconductors have shown promising optoelectronic properties as further revealed by UV-Vis absorption spectroscopy, cyclic voltammetry, and theoretic calculation.



Diastereoselective Synthesis of 1, 10-Dihydropyrrolo[1, 2-a][1, 10]phenanthroline Derivatives via 1, 3-Dipolar Cycloaddition Reaction

LIU Zhen-ming, FANG Jun, YAN Chao-guo

2013, 29(6):  1089-1093.  doi:10.1007/s40242-013-3224-2

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The functionalized 1,10-dihydropyrrolo[1,2-a][1,10]phenanthroline derivatives were synthesized in good yields and with high diastereoselectivity by 1,3-dipolar cycloaddition reactions of N-phenacylphenanthrolinium bromides or N-ethoxycarbonylmethylene phenanthrolinium bromide with various nitrostyrenes in acetonitrile at room temperature in the presence of triethylamine.



Synthesis and Characterization of Two [2]Catenanes Based on Phenylene-diacetylene Crown Ethers

CHEN Mu-juan, ZHOU Song-gen, LI Mei, LEI Chun-yan, XIAO Rui, JIANG La-sheng

2013, 29(6):  1094-1097.  doi:10.1007/s40242-013-3218-0

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Two charged donor-acceptor [2]catenanes were synthesized by the cyclization of the π-acceptor 1,1'-[1,4-phenylenebis-(methylene)]bis(4,4'-bipyridinium)bis(hexafluorophosphate)(2) and bis(bromomethyl)benzene with the templates of the π-donor phenylene-diacetylene crown ethers 1a and 1b in the yields of 31%, 35%, respectively. The mass spectra, ¹H and ¹³C NMR spectra confirm that the phenylene-diacetylene crown ethers, with a nonaromatic π-system, successfully template the cyclization of CBPQT⁴⁺. The X-ray crystallography analysis shows that the CBPQT⁴⁺ ring encircles around the phenylene motif of the crown ethers, leaving the 1,3-butadiyne fragment out of the cavity of CBPQT⁴⁺ ring. The mechanically interlocked structure of [2]catenanes was stabilized by the cooperative effects of π-stacking and hydrogen bonding interactions.



Synthesis and Characterization of Pyrazoleanthrone Derivatives as Aurora A Kinase Inhibitors

SUN Xiao-xiao, SUN Tao, WANG Tai-yi, ZHANG Yan, LIU Hui-juan, WANG Quan, NIU Guo-jun, LIU Wei, ZHOU Hong-gang, YANG Cheng

2013, 29(6):  1098-1103.  doi:10.1007/s40242-013-3216-2

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Aurora A is a cell cycle kinase linked to cancer. For the purpose of finding biologically active of novel compounds and providing new ideas for drug-design, we performed virtual screening in commercially available databases and got pyrazoleanthrone with promising inhibitory activity against Aurora A. Optimization of solvent accessible C7 position of pyrazoleanthrone made us get thirteen target compounds. These pyrazoleanthrone derivatives were evaluated by Aurora A inhibition assays in vitro. The results show that some target compounds could inhibit Aurora A kinase. Meanwhile, these title compounds were tested in vitro against hepatocellular carcinoma(HepG2) cells by the 3'-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide(MTT) method, showing that most of them had inhibitory potency. The inhibition rate of compound 6h was about 80% against HepG2 cells, and the IC₅₀ value was 17.4 μmol/L, which would be considered for further study.



Synthesis and Anti-leukemia Evaluation of Tetrahydro-4H-pyrano[3, 2-c]pyridines and Corresponding Anti-CD14 Monoclonal Antibody Conjugates

SUN Chuan-wen, WANG Jing, PANG Chun-cheng, LI Jing, XIAO Di

2013, 29(6):  1104-1109.  doi:10.1007/s40242-013-3211-7

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A series of novel tetrahydro-4H-pyrano[3,2-c]pyridines(3a―3p) were synthesized and found to possess potent antiproliferative activity against leukemia K562 cells in vitro. Preliminary bioassay indicates that compounds 3a and 3e afford the best activity, the IC₅₀ values of them were 6.93 and 7.51 μg/mL, respectively, which were lower than that of the anticancer drug 5-FU(IC₅₀=8.56 μg/mL). To reduce the toxicity of compounds 3a―3p to the proliferation of normal hematopoietic cells, a tumor targeted CD14 monoclonal antibody(McAb) was used in conjugation with compounds 3a―3p to get conjugates 4a―4p, respectively. The inhibitory activities of conjugates 4a―4p toward K562 cells were discovered to approach those of compounds 3a―3p. In the presence of CD14 McAb, tumor cells were found to be much more susceptible to conjugates 3a―3p than normal hematopoietic cells. Therefore, the toxi-city of conjugates 4a―4p to normal hematopoietic cells declined obviously. For example, as for the toxicity of compound 3a compared with that of compound 4a, the value of IC₅₀ increased from 35.90 μmol/L to 39.52 μmol/L.



Synthesis, Docking and Biological Evaluation of Isoquinolonic Acid Derivatives

ZHANG Hao, ZHENG Yu-qiong, GUO Jing, WANG Xiao-ming, YANG Yong-hua

2013, 29(6):  1110-1114.  doi:10.1007/s40242-013-3149-9

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A series of isoquinolonic acid derivatives(4a-4o) was synthesized via one-pot synthesis for their anti-tumor activity. The structures of all the targeted compounds were confirmed by ¹H nuclear magnetic resonance (¹H NMR) spectrometry and mass spectrometry(MS). The anti-tumor activities of compounds 4a-4o against MG63(human osteosarcoma cells) and B16-F10(mouse melanoma cells) were examined. To evaluate the antitumor effect of the as-synthesized compounds, we compared the half maximal inhibitory concentration(IC₅₀) of compounds 4a-4o to that of camptothecin(CPT) which appeared to be active against a broad range of human cancers. Among all the compounds, compound 4l shows the most potent biological activity against MG63 cells[IC₅₀=(2.16±0.26) μmol/L] and B16-F10 cells[IC₅₀=(6.95±0.24) μmol/L], thus providing useful information for the antitumor activity and potential practical use of isoquinolonic acid compounds. In addition, we screened out an efficient compound(4l) that shows potential inhibit activity against Topoisomerase I(Topo I) by docking simulation.



Simple and Efficient Procedure for Highly Diastereoselective Synthesis of trans-1, 1-Disubstituted-2, 6-diarylcyclohexane-4-ones

YU Ya-qin, WANG Zhong-liang

2013, 29(6):  1115-1118.  doi:10.1007/s40242-013-3136-1

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A simple and efficient method has been developed for highly diastereoselective synthesis of trans-1,1-disubstituted-2,6-diarylcyclohexane-4-ones from dibenzalacetone and malononitril with trans-1,2-diami-nocyclohexane as catalyst. The substrate 1,5-diaryl-1,4-pentadien-3-ones and active methylene compounds proceeded to give the products with good to excellent yield within a short time.



Synthesis of Dihydrobenzofuran Neoligans Licarin A and Dihydrocarinatin as Well as Related Triazolylglycosides

LIU Shuang-yan, WANG Gang-qiang, LIANG Zhi-ying, WANG Qiu-an

2013, 29(6):  1119-1124.  doi:10.1007/s40242-013-3131-6

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Two natural dihydrobenzofuran neolignans licarin A(1) and dihydrocarinatin(2) were systhesized from isoeugenol with Ag₂O-catalyzed biomimetic oxidative coupling as the key step. Four novel dihydrobenzofuran triazolylglycoside(3―6) were achieved in good yields via Cu(I)-catalyzed azide-alkyne cycloadditions of licarin A terminal alkynes with different azide acetylated sugar and deacetylation with sodium methoxide in anhydrous methanol. The structures of all the compounds synthesized were determined by elemental analysis, MS, ¹H NMR and ¹³C NMR. And the inhibition activity of synthesized compounds on α-glucosidase was determined by in vitro experiments. The results show that triazolyglycosides 3, 4, 5 and 6 show moderate inhibitory activity on α-glucosidase.



Design, Synthesis and Antitumor Activity in vitro of a Series of 3-Arylcoumarins

LIU Zhi-hui, LI De-jun, JIANG Dan, XIAO Chuan, SONG Zhi-guang, JIN Ying-hua

2013, 29(6):  1125-1128.  doi:10.1007/s40242-013-3107-6

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A new series of 7-substituted 3-arylcoumarins was designed, synthesized and evaluated as novel antitumor agents in vitro. It was found that several compounds of them exhibit activity in vitro against SK-HEP-1(hepatocellu-lar carcinoma), HepG2(hepatocellular carcinoma) and SGC7901(gastric carcinoma) cell lines to some extent. Moreover, compounds 5a, 5b, 6a and 6b have better activity against HeLa(cervical carcinoma) cell and their half maximal inhibitory concentration(IC₅₀) values are less than 10 μmol/L.



Synthesis and Properties of Symmetrical Aryl Linked BODIPY Dyads

WANG Bang-ying, ZHAO Hong-bin, LIAO Jun-xu, XU Yong-jun

2013, 29(6):  1129-1133.  doi:10.1007/s40242-013-3090-y

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Three novel symmetrical 4,4'-difluoro-4-bora-3a,4a-diaza-sindacene(BODIPY) derivatives were synthesized via a general and efficient protocol. These BODIPY dyads bear a diverse aryl linker bridge in the middle and two BODIPY units at the termini. The photophysical properties of these dyads were investigated by ultraviolet-visible(UV-Vis) absorption and emission spectroscopy. And their electrochemical properties were studied by cyclic voltammetry. The absorption of these dyads showed slightly blue shift and the intramolecular charge transfer(ICT) state underwent ultrafast direct surface crossing to the ground state with high degree of rotational freedom. The results will be useful for the further functionalization of these novel symmetrical BODIPY derivatives.



Synthesis and Biological Activity of Novel Anthranilic Diamides Containing N-Substituted Arylmethylene Moieties

ZHANG Xiu-lan, LIU Ai-lin, ZHAO Yu, XIONG Li-xia, LI Zheng-ming

2013, 29(6):  1134-1139.  doi:10.1007/s40242-013-3038-2

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A series of novel anthranilic diamides containing N-substituted arylmethyl moieties was designed and synthesized, in which the bond distance and conjugation pattern between pyrazole and pyridine rings contained in Chlorantraniliprole were changed. Their structures were confirmed by ¹H NMR, IR, elemental analysis or high resolution mass spectromentry(HRMS), and the conformation of compound 4d was confirmed by X-ray diffraction. The preliminary bioassay results indicate that all the target compounds exhibited moderate insecticidal activity against oriental armyworm at 200 mg/L and some of them presented favorable antitumor activities against human lung cancer cells(A549), liver cancer cells(Bel7402) and colon cancer cells(HCT-8) in vitro by microculture tetrazolium(MTT) method, among which compound 6j afforded the best anti-proliferative activity at 5 μg/mL.



Novel Stereoselective Carbonyl Reductase from Kluyveromyces marxianus for Chiral Alcohols Synthesis

LI Hai-dong, SUN Zhi-hao, NI Ye

2013, 29(6):  1140-1148.  doi:10.1007/s40242-013-3286-1

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A novel nicotinamide adenine dinucleotide phosphate(NADPH)-dependent carbonyl reductase from Kluyveromyces marxianus(KmCR) was identified, which can convert various prochiral ketone esters and ketone substrates to their corresponding chiral alcohols. KmCR was over-expressed in E. coli BL21(DE3), purified to homogeneity, and characterized. The purified enzyme exhibits the highest activity at 40℃ and pH=6.0. Based on the gel filtration and sodium dodecyl sulfate-polyacrylamide gel electrophoresis(SDS-PAGE) analysis, the monomeric protein was determined to have a molecular weight of approximate 39000. V_max and K_m of KmCR are 4.28 μmol·min^-1·mg^-1 and 0.41 mmol/L for ketone ester substrate ethyl 2-oxo-4-phenylbutyrate(OPBE), 3.09 μmol·min^-1·mg^-1 and 1.21 mmol/L for cofactor NADPH, respectively. Cofactor recycle was achieved by co-expression of KmCR and glucose dehydrogenase(GDH) in E. coli. Recombinant E. coli harboring KmCR and GDH showed moderate asymmetric reduction activity towards various α-and β-ketoesters, diaryl ketone substrates. In an aqueous/butyl acetate biphasic system, the whole-cell biocatalyst was used to prepare ethyl (R)-2-hydroxy-4-phenylbutanoate[(R)-HPBE] in an e.e. of 99.5% with a space-time yield of 433.6 g·L^-1·d^-1 and a yield of 80.3% at 270 g/L OPBE.



In situ Analysis of Na and K in a Laminar Premixed Flame by Laser-induced Breakdown Spectroscopy

LI Yu, ZHANG Han-zhuang, LI Zhong-shan, LI Hong-dong, ZHANG Chun-wei, HU Chang-hong

2013, 29(6):  1149-1152.  doi:10.1007/s40242-013-3268-3

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Laser-induced breakdown spectroscopy(LIBS) was used to in situ monitor the concentration of alkali elements in combustion environments. Particular efforts were made to optimize the temporally resolved spectra of Na and K elements. Calibration curves were constructed by relating the intensities of the specific lines to the corresponding elemental concentrations. The detection limits of Na and K elements were found to be temperature-dependent. The results indicate that LIBS can be a powerful tool for in situ monitoring Na and K concentrations in combustion environments.



Molecular Modeling and Docking of Mannose-binding Lectin from Lycoris radiata

ZHU Qian-kun, ZHU Meng-li, ZOU Jia-xin, FENG Pei-chun, FAN Gao-tao, LIU Zu-bi, WANG Wan-jun

2013, 29(6):  1153-1158.  doi:10.1007/s40242-013-3259-4

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Lycoris radiata mannose-binding lectin(LRL) is a protein which binds mannose residues specifically. The maturation peptide and three mannose-binding domains(residues 49―57, 80―88 and 113―121) of LRL were identified by sequence analysis. The 3D structure of LRL constructed by homology modeling shaped a fistular triangular prism. Three flanks of the prism are mainly composed of β-sheets and each flank has a mannose-binding domain. According to the docking and dynamics simulation, the bindings of residues 49―57 and 80―88 with mannose are more stable than that of residues 113―121 with it. The key residues for binding mannose are Gln80, Asp82, Asn84 and Tyr88. The study preliminarily analyzed the interaction sites and mechanism of LRL with mannoses, which could be useful for the study on insect-resistance and related drug discovery of LRL.



Scattering Resonance State of Br+HBr(v=0)→BrH(v’=0)+Br Reaction Explored by Partial Potential Energy Surface Method

LU Xi, ZHANG Ming-tao, CAI Zheng-ting, SUN Xiao-min

2013, 29(6):  1159-1163.  doi:10.1007/s40242-013-3254-9

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The partial potential energy surface(PPES) of Br+HBr(v=0)→BrH(v'=0)+Br was designed by coupling the vibration energy and the minimum energy of the corresponding reaction path, V_mep. All the calculations were performed at the theoritical level of QCISD(T)/6-311++G^**//MP2/6-311++G^**. Based on the analysis of PPES, the dynamic "Eyring Lake" mechanism gave birth to the scattering resonance state. The resonance energy was also obtained via PPES. Then a lifetime matrix of the resonance state was established by solving the translational wave-function via the numerical propagation method. Then the reaction resonance lifetime was calculated to be 125 fs. It is in good agreement with the experimental result.



Synthesis of Nitroanilines Catalyzed by Horseradish Peroxidase in the Presence of NaNO₂ and H₂O₂

LIU Cong, DAI Rong-ji, LIN Jie, SUN Jian-hua, CHEN Shi, DENG Yu-lin

2013, 29(6):  1164-1166.  doi:10.1007/s40242-013-3251-z

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The synthesis of nitroanilines catalyzed by horseradish peroxidase(HRP) in the presence of sodium nitrite and hydrogen peroxide was investigated. o-Nitroaniline and p-nitroaniline were found in the nitrated products. 2-Aminotoluene and 4-aminotoluene could also be nitrated to give corresponding nitrated products. This protocol has great potentials to open new avenues useful for the synthesis of nitroaniline and its derivatives.



Phase Equilibria in Al-Ca-Li System：a Thermodynamic Description

WANG Kun, YIN Hui-qin, CHENG Jin-hui, ZUO Yong, XIE Lei-dong

2013, 29(6):  1167-1172.  doi:10.1007/s40242-013-3219-z

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Relations of equilibrium phases in the Al-Ca-Li system were calculated by means of the CALPHAD (calculation of phase diagram) method. The reported thermodynamic model parameters for all the constituent binary systems were directly used in the present calculation. A novel thermodynamic description for the three ternary intermetallic compounds(τ₁, τ₂ and τ₃) was made on the basis of experimental phase equilibria in the Al-Ca-Li system. Comparison between the calculated and experimental phase equilibria shows that we have successfully derived a set of self-consistent thermodynamic parameters for the Al-Ca-Li system. These parameters were then used for the prediction of the selected isothermal and isopleth sections and projected liquidus surface of this ternary system over the entire composition range.



Trichloroethylene Dechlorination by Copper-contained Zero-valent Iron Slurry

LI Hai-jun, QIU Hua, ZHANG Lan-ying, LIU Na, ZHU Bo-lin

2013, 29(6):  1173-1179.  doi:10.1007/s40242-013-3165-9

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Zero valent iron technology has been widely used for treating contaminated wastewater these years. However, it always results in inefficiency in the processes of drying and storage due to oxidation and passivation. This could be avoided by in situ synthesized zero valent iron slurry in an emergency if it possesses the same performance as zero valent iron. In this study, iron slurry was synthesized and directly used for dechlorinating trichloroethylene to measure its degradation efficiencies and properties. Results show that 2%(mass ratio) copper-contained zero-valent iron slurry exhibits the optimal performance compared with the other iron slurries. Batch experiments indicate that factors such as the concentration of trichloroethylene, pH, dissolved oxygen and equilibrium to a certain extent affect the reduction of trichloroethylene by 2%(mass ratio) copper-contained zero-valent iron slurry. Persistent, high-efficiency degradation performance could last 7 cycles. These demonstrate that the application of copper-contained zero-valent iron slurry in treating trichloroethylene-contained wastewater is realistic.



Characterization and Three-dimensional Structural Modeling of Humic Acid via Molecular Mechanics and Molecular Dynamic Simulation

ZHAO Nan, LÜ Yi-zhong, LI Guang-jun

2013, 29(6):  1180-1184.  doi:10.1007/s40242-013-3156-x

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The humic acid(HA) sample obtained from the alluvial soil was characterized by elemental composition, pyrolysis gas chromatography-mass spectrometry(Py-GC-MS) and solid-state ¹³C nuclear magnetic resonance (¹³C NMR) spectroscopy. There is high fat content and a few nitrogen-containing functional groups in HA. Py-GC-MS demonstrates the characterization and structural identification of HA. One long list of identified pyrolysis products was proposed for the construction of conceptual model of HA. Solid-state ¹³C NMR data indicate there are higher values of alkyl-C, O-alkyl-C and aryl-C in HA. The elemental composition, structural carbon distribution and ¹³C NMR spectroscopy of simulated HA are consistent with those of experimental HA. HyperChem^® was used to simulate the three-dimensional molecular structure of the monomer, which was optimized by the molecular mecha-nics of the optimized potential for liquid simulations(OPLS) force field and molecular dynamics simulation to get the stable and balanced conformation. The deprotonation process study depicts that the degree of ionization of HA gets deeper, while the electronegativity of HA and the energy of van der Waals(vdW) increase. Moreover, the 3D structure of humic acid with-4 charges is the most stable. The deprotonation process is an endothermic process.



Photovoltaic Performance and Charge Recombination Dynamics of P3HT/PCBM Blend Heterojunction

YAO Jin-bo, WANG Ying-hui, ZHANG Han-zhuang

2013, 29(6):  1185-1188.  doi:10.1007/s40242-013-3152-1

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We prepared the polymer solar cell based on poly(3-hexylthiophene)(P3HT)/fullerene derivative PCBM(PCBM=[6,6]-phenyl-C61-butyric acid methyl ester) heterojunction and investigated the irradiation intensity-dependent charge recombination dynamics of heterojunction employing nanosecond transient absorption spectroscopy with bias light so as to simulate the photophysical process in heterojunction when the photovoltaic device is on operation. The experimental data exhibit that the yield of free charges gradually decreases and the loss of mobile carriers originated from bimolecular recombination simultaneously increases as the irradiation intensity gradually enhances. This indicates that the polymer solar cell is much suitably used at a low irradiation intensity.



Mean Activity Coefficients of KCl in the KCl-K₂B₄O₇-H₂O Ternary System at 308.15 K by EMF Method

ZHONG Si-yao, SANG Shi-hua, ZHANG Jun-jie

2013, 29(6):  1189-1192.  doi:10.1007/s40242-013-3139-y

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The mean activity coefficients of KCl in a KCl-K₂B₄O₇-H₂O ternary system were experimentally determined at 308.15 K by the electromotive force measurement(EMF) via a battery cell without a liquid junction: K-ISE|KCl(m₁), K₂B₄O₇(m₂)|Cl-ISE(ISE=ion selective electrode) in a total ionic strength of from 0.01 mol/kg to 1.00 mol/kg at different ionic strength fractions of K₂B₄O₇ with y_B=0, 0.200, 0.400, 0.600 and 0.800. K-ISE and Cl-ISE presented a good Nernst effect, which implies that this method could be used to measure the activity coefficients of an electrolyte in the above system. The Harned rule was fitted to the experimental data, the Harned coefficients and the Pitzer single-salt ion parameters of KCl were evaluated, and the relationship diagrams between the mean activity coefficient of KCl and the ionic strength fraction(y_B) were drawn. The mean activity coefficients of KCl(γ_±KCl) decreased monotonically with the increase of I. The experimental results obeyed the Harned rule well.



Characterization and Properties of a New Amorphous Small-molecule Material Containing Both Donor andAcceptor Moieties for Photovoltaic Application

ZHAO Yang, ZHANG Feng-ling, ZHANG Ming, MA Yu-guang

2013, 29(6):  1193-1198.  doi:10.1007/s40242-013-3122-7

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A new amorphous small-molecule material, in which the electron-donating carbazole units are connected to the backbone by flexible side chains, has been synthesized and utilised in the photovoltaic(PV) field. This material exhibits the amorphous feature, higher thermal stability and good film forming ability. The influence of the heat-treatment on the morphology and the performance of PV devices were studied. Eventually, a relatively high photovoltaic conversion efficiency was achieved. At the same time, the PV device displayed an ideal open-circuit voltage(over 1 V) which is very close to the upper limit of its theoretical value.



Robust High Temperature Sensor Probe Based on a Ni-coated Fiber Bragg Grating

WANG Chuang, ZHU Feng, REN Lin, LI Ai-wu, CHEN Chao, YANG Rui, GUO Jing-chun, XUE Yang, ZHANG Xuan-yu, ZHU Cong-cong, CHEN Qi-dai, YU Yong-sen

2013, 29(6):  1199-1202.  doi:10.1007/s40242-013-3114-7

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A robust high temperature sensor probe based on a Ni-coated fiber Bragg grating(FBG) was fabricated by Ni electroplating of femtosecond laser written FBG. The probe can resist high temperature up to 800℃ with a high sensitivity of 32.2 pm/℃. It also has a good mechanical strength even after high temperature annealing. The thermal strain of the probe was simulated by the finite element method(FEM). The Bragg resonant wavelength shift with temperature and its sensitivity change with the thickness of the Ni-coated layer were also calculated.



Dynamic Properties of Polyampholyte Hydrogel Elucidated by Proton NMR Spin-spin Relaxation Time

LU Cui-ge, XU Kun, LI Wen-bo, LI Peng-chong, TAN Ying, WANG Pi-xin

2013, 29(6):  1203-1207.  doi:10.1007/s40242-013-3151-2

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¹H spin-spin relaxation time(T₂) measurement of polyampholyte hydrogel poly(methylacrylic acid-acryloyloxyethyl trimethylammonium chloride)[P(MA-DAC)] in different pH, ionic strength and temperature was carried out to reveal the molecular mobility. Spontaneous volume transition of the polyampholyte hydrogel was also investigated by spin-spin relaxation time measurement. Meanwhile T₂ and the proton component fraction were acquired to study the swelling behaviour of the hydrogel. Moreover the changes of T₂ characterized the molecular mobility of polyampholyte hydrogel in various swelling states. And the results suggest that the mobility of the main chains and a few free side chains(the long T₂) of P(MA-DAC) was dominated by the mesh size in the hydrogel network, depending on the swelling ratio(Q) and the mobility of the side chains(the short T₂) was influenced by electrostatic interaction between different charges in polymer side chains. Finally the T₂ measurements of P(MA-DAC) hydrogel in the spontaneous swelling-deswelling process demonstrated the electrostatic interaction of the charged side chains caused deswelling behavior. At the same time, the mobility state transition temperature of the charged side chains was also studied by the ¹H spin-spin relaxation time measurements, and the transition activation energy of the side chains is 2.72 kJ.



Efficient Hybrid Photovoltaic Devices Based on in-situ Electrochemical Copolymerization of 3-Methylthiophene and Bithiophene into Pores of Nanocrystalline TiO₂

LU Sheng-li, GENG Rui

2013, 29(6):  1208-1213.  doi:10.1007/s40242-013-3116-5

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Novel organic and inorganic hybrid photovoltaic devices were fabricated by in-situ electrochemical copolymerization of 3-methylthiophene(3MT) and bithiophene(BT) into the pores of nanostructured TiO₂ sintered on fluorine-doped tin oxide(FTO) substrate. The photoactive layer was investigated by Fourier transform infrared(FTIR) spectroscopy, ultraviolet-visable(UV-Vis) spectrometer, scanning electron microscope(SEM) and cyclic voltammogram characterization. Device efficiency based on different molar feed ratios of 3MT and BT during electrochemical polymerization, and the effect of in-situ copolymer state(doped by electrolyte and de-doped) were measured and compared. Under the solar illumination of 100 mW/cm²(AM1.5), an optimized device efficiency of 0.938% was obtained when the molar ratio of 3MT to BT was 500:1, polymerization time was 500 s and the system was in doped copolymer state, respectively. The mechanism of overall photovoltaic parameter improvement was discussed.



Silver Chloride Loaded Mesoporous Silica Particles and Their Application in the Antibacterial Coatings on Denture Base

LI Xian-liang, ZUO Wei-wen, LUO Meng, SHI Zuo-sen, CUI Zhan-chen, ZHU Song

2013, 29(6):  1214-1218.  doi:10.1007/s40242-013-3092-9

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Thiol-functionalized MCM-41 type mesoporous silica particles(MSPs) were prepared and loaded with silver chloride to act as antibacterial agents. The antibacterial activity of the silver chloride loaded MSPs(AgCl-MSPs) was evaluated by the minimum bactericidal concentration(MBC) against Candida albicans(ATCC 10231). The AgCl-MSPs with the highest antibacterial activity were then dispersed in hybrid coatings with different mass ratios to fabricate antibacterial coatings. The antibacterial activity of the coatings was tested against Candida albicans(ATCC 10231) and Streptococcus mutans(ATCC 25175). The resulting antibacterial coatings exhibited high antibacterial activity, good adhesion to the substrate and high hardness.



In situ Molecular Self-assembly and Sensitive Label-free Detection of Streptavidin via a Wavelength Interrogated Surface Plasmon Resonance Sensor

YU Yong-jiang, ZHOU Ying, LI Qiu-shun, YANG Yan, SHI Jian-guo, LI Ming-yu, YAO Wei-guo, WANG Jun-nan, DONG Wen-fei, QI Zhi-mei

2013, 29(6):  1219-1224.  doi:10.1007/s40242-013-3085-8

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The sensing sensitivity of wavelength interrogated surface plasmon resonance(WISPR) biosensor is improved by self-assembly of polyelectrolyte multilayer(PEM) film of poly(allylamine hydrochloride)(PAH)/ poly(sodium-p-styrenesulfonate)(PSS) on the Au film coated glass chip via the layer-by-layer(LBL) technique. The home-made WISPR with Krestchmann configuration consists of a tungsten-halogen lamp as a photon source and a charge coupled device(CCD) camera as the detector. The influence of PEM film thickness on the optical properties of WISPR biosensors was investigated theoretically and experimentally. In order to achieve higher sensing sensitivity, the PEM film thickness has to be designed as ca.14 nm at an Au layer thickness of 50 nm and an incidental angle of 11.8°. Furthermore, the PEM coated WISPR biosensor can serve as highly sensitive biosensor, in which the biotin-streptavidin is used as bioconjugate pair. After deposition of the PEM film of (biotin/PAH)(PSS/PAH)₃, the mo-dified WISPR biosensor is more sensitive to the low concentration(<0.01 mg/mL) of streptavidin. And the sensing sensitivity can be further increased by one order of magnitude compared with that of the biotin/PAH coated WISPR biosensor. Thus, such low-cost, high-performance and efficient PEM-coated WISPR biosensors have great potentials in a diverse array of fields such as medical diagnostics, drug screening, food safety analysis, environmental monito-ring, and homeland security.



Synthesis and Characterization of Novel Sulfonated Polyimides from 4, 6-Bis(4-aminophenoxy)-naphthalene-2-sulfonic Acid

LI Yu-han, WANG Wei-jian, JIN Ri-zhe, GAO Lian-xun

2013, 29(6):  1225-1228.  doi:10.1007/s40242-013-3076-9

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A novel sulfonated diamine monomer, 4,6-bis(4-aminophenoxy)-naphthalene-2-sulfonic acid(BAPNS), was synthesized. A series of sulfonated polyimide copolymers was prepared from BAPNS, 1,4,5,8-naphthalenetetra-carboxylic dianhydride(NTDA) and nonsulfonated diamine 4,4'-diaminodiphenyl ether(ODA). Flexible, transparent, and mechanically strong membranes were obtained. The novel sulfonated polyimide(SPI) membranes show higher conductivity, for example, SPI-100 shows a conductivity of 0.0698 S/cm at 80℃(SPI-X: X refers to molar fraction of BAPNS). The membranes exhibit the permeability of methanol from 2.18×10^-7 cm²/s to 2.57×10^-7 cm²/s, which is much lower than that of Nafion(2.00×10^-6 cm²/s). The copolymers were thermally stable up to 330℃. The sulfonated polyimide copolymers also show reasonable mechanical strength; for example, the maximum tensile strength at break of the sulfonated polyimide copolymer with 100%(molar fraction) BAPNS is 1.35 GPa under high moisture conditions. The optimum concentration of BAPNS was found to be 100%(molar fraction) from the view point of proton conductivity, methanol permeability, and membrane stability.