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25 May 2011, Volume 27 Issue 3

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Cover and Content of Chemical Research in Chinese Universities Vol.27 No.3(2011)

2011, 27(3):  0. 

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Articles

Development of NAMI-A-loaded PLGA-mPEG Nanoparticles: Physicochemical Characterization, in vitro Drug Release and in vivo Antitumor Efficacy

YANG Yong-guang, LIU Du, XIA Yu, ZHOU Yan-hui, ZHONG Xue-yun* and LIU Jie*

2011, 27(3):  345-349. 

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NAMI-A has showed extraordinary activities against metastatic tumors. However, the hydrolysis of DMSO from NAMI-A could reduce anti-metastatic activity. To enhance the circulation time and the anti-metastatic effect of NAMI-A, we first synthesized the NAMI-A-loaded nanoparticles. NAMI-A-loaded nanoparticles were prepared by the double emulsion method and characterized by scanning electron microscopy for surface morphology, laser light scattering for size and zeta potential for surface charge. Controlled release of NAMI-A was observed in a sustained manner. Compared with free NAMI-A, NAMI-A -loaded nanoparticles exhibited superior antitumor effect by delaying tumor growth in T739 mice. PLGA-mPEG nanoparticles are promising for further studies as drug delivery carriers.



Synthesis and Characterization of Mesoporous Titanium Dioxide Spheres

GULI Mi-na, CHEN Yu-ning and LI Xiao-tian*

2011, 27(3):  350-353. 

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Mesoporous titanium dioxide spheres were synthesized by a convenient solvothermal method at room temperature with tetraethyl titanate as a precursor. Investigation by means of X-ray diffraction(XRD), transmission electron microscopy(TEM), scanning electron microscopy(SEM), and N2 adsorption-desorption isotherms confirms that the sample has a mesostructure with a higher specific surface area and shows that the mesoporous TiO2 spheres have a diameter of 2 μm, the average pore size is about 5.9 nm, and the BET surface area and specific pore volume are about 236 m2/g and 2.116 cm3/g, respectively. The anatase and rutile mesoporous TiO2 spheres calcined at 700 °C show much better photocatalytic activity than the samples calcined at other temperatures and is comparable to an  uncalcined sample in the photodegradation of Methyl Blue(MB) under the UV irradiation.



Synthesis, Structure and Luminescent Property of a Zinc(II) Coordination Polymer Incorporating Flexible Cyclohexane-1,2,3,4,5,6-hexacarboxylate Ligand

WANG Jing*, LIU Zhao-qing and SU Ting-ting

2011, 27(3):  354-357. 

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The hydrothermal reaction of Zn(NO3)2?4H2O, cyclohexane-1,2,3,4,5,6-hexacarboxylic acid hydrate (H6LI?H2O, cis-conformation LI: a,e,a,e,a,e) and 2,2'-bpy yielded a new coordination polymer [Zn2(H2LII)(2,2'-bpy)]? 2H2O(trans-conformation LII: e,e,e,e,e,e), which was characterized by single-crystal X-ray diffraction, elemental analysis, IR and XRPD(X-ray powder diffraction). This complex crystallized in the triclinic system, with P1?? space group and parameters a=0.66922(5) nm, b=0.97291(8) nm, c=1.22184(9) nm, α=99.0020(10)o, β=99.1300(10)o, γ=99.1910(10)o, V= 0.76176(10) nm3 and Z=2. The structure is a three-dimensional supramolecular network based on linear coordination chains through π-π stacking and hydrogen bonding interactions. The confromation of the starting ligand H6LI transfromed to the H2LII. The complex emits strong luminescence at room temperature.



Synthesis, Characterization and Inhibition Effects of Vanadium Substituted Dawson-type Heteropoly Acids(Mo, P)

YIN Yan-bing, YANG Yu-lin*, FAN Rui-qing, ZHU Yang-qing and SUN Ji-ru

2011, 27(3):  358-360. 

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Four new vanadium substituted Dawson-type heteropoly acids H7[P2Mo17VO62]·39H2O(1), H8[P2Mo16V2O62]·41H2O(2), H9[P2Mo15V3O62]·51H2O(3) and H8[P2Mo14V4O62H2]·45H2O(4) were prepared respectively. Their structures were determined by IR and ICP. The inhibition effects of vanadium substituted Dawson-type heteropoly acids(Mo, P) on free radical polymerization of methyl methacrylate(MMA) were investigated by dilatometry. The results show that the rate of the polymerization of MMA decreases and the inhibition effects of the four heteropoly acids reach the inhibitor performance of hydroquinone at a certain ratio.



Purification Technology and Antimicrobial Activity Analysis of Antimicrobial Peptide from Ovotransferrin

ZHANG Tie-hua, ZHENG Jian, YE Hai-qing, YU Ya-li, ZHAO Ping and LIU Jing-bo*

2011, 27(3):  361-365. 

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Antibacterial peptides mixture purified from Ovotransferrin by pepsin digest was used as the raw material. Peptide sections with good antibacterial activity were determined after bacteriostasis experiments, its molecular weight and amino acid composition were analyzed. The results of experiments indicate that with Sephadex G-50 and distilled water as mobile phase, detection wavelength 220 nm, flow rate 1.5 mL/min, sample density 0.2 g/mL, and volume 0.2 mL are the optimal conditions. Bacteriostasis experiments of the fraction of purified peaks were carried out and the result was: peak 1>peak 3>peak 2; the molecular weight of peak 1 was about 3015 by high performance liquid chromatography; active peptide possessed positive charges by amino acid analysis, its cationic characteristics are in accordance with the nature of antimicrobial peptides.



Determination of Trace Amounts of Nickel(II) by Graphite Furnace Atomic Absorption Spectrometry Coupled with Cloud Point Extraction

SHAH Syed Mazhar, WANG Hao-nan and SU Xing-guang*

2011, 27(3):  366-370. 

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A new method based on the cloud point extraction(CPE) for separation and preconcentration of nickel(II) and its subsequent determination by graphite furnace atomic absorption spectrometry(GFAAS) was proposed, 8-hydroxyquinoline and Triton X-100 were used as the ligand and surfactant respectively. Nickel(II) can form a hydrophobic complex with 8-hydroxyquinoline, the complex can be extracted into the small volume surfactant rich phase at the cloud point temperature(CPT) for GFAAS determination. The factors affecting the cloud point extraction, such as pH, ligand concentration, surfactant concentration, and the incubation time were optimized. Under the    optimal conditions, a detection limit of 12 ng/L and a relative standard deviation(RSD) of 2.9% were obtained for Ni(II) determination. The enrichment factor was found to be 25. The proposed method was successfully applied to the determination of nickel(II) in certified reference material and different types of water samples and the recovery was in a range of 95%―103%.



Analysis of Phospholipids in Crucian Carp(Carassius auratus) Muscle by Offline HPLC-MALDI-TOF MS

LI Guo-chen , WANG Yan-hong*, WU Ren-an and WANG Shi-cheng

2011, 27(3):  371-374. 

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The interest in the analysis of phospholipids(PLs), especially phosphatidylcholine(PC), has been increa- sing due to the importance of them in biochemistry as well as in industry. A method was reported based on the offline combination of MALDI-TOF MS and normal-phase HPLC for analyzing PLs extracted from crucian carp. Total PLs of crucian carp were extracted and then separated by HPLC before the collected subfractions were analyzed by MALDI-TOF MS. The mass spectra obtained show peaks of H+, Na+ and K+ adducts of PC molecules. It is shown that the prior separation of PLs by HPLC is highly necessary to remove the signal suppressing and to avoid the possible overlapping. With this method, 9 possible PC molecules in crucian carp and the corresponding fatty acid compositions were given from the well-resolved mass spectra.



Simultaneous Determination of Two Types of Active Components with Different Physicochemical Properties in Kushen by HPLC-UV

ZHANG Yu-feng, ZHAO Qin-qin, SHAO Qin and FAN Xiao-hui*

2011, 27(3):  375-379. 

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A simple, reliable and accurate high performance liquid chromatography(HPLC) coupled with a UV   detector at varied wavelength was developed for the quantitation of two types of anti-carcinogenic compounds, namely, Kushen alkaloids(KS-As) and Kushen flavonoids(KS-Fs), in Kushen. Their remarkable difference in physicochemical properties was circumvented by integrated optimization of column and mobile phase. The separation was achieved on an alkaline-resisting C18 column via gradient elution with acetonitrile(ACN) and 0.025%(volume ratio) diethylamine(DEA) in water as mobile phase. The flow rate was 0.7 mL/min, and the column temperature was maintained at 35 °C. UV detection wavelength was set at 225 nm to monitor KS-As, and then changed to 335 nm for KS-Fs at 26th min, which was kept for 30 min before returning to the original wavelength. All the calibration curves show good linearity(r2>0.999) within test ranges. The intra- and inter-day precision values of these components were less than 3.82%, and the average recovery rates obtained were in a range of 97.24%―102.64% for all the samples with RSD below 3.94%. This assay was successfully applied to determining the major active components in commercial herbal samples of Kushen. Moreover, the possible relationship between sample and the geographical region was visualized based on the contents of the 6 compounds in the light of principal component analysis(PCA). The results suggest that the proposed method facilitates the quality control of Kushen.



Intestinal Transport and Biotransformation of Resibufogenin and Cinobufagin in Chan Su via HPLC/APCI-MSn

HAN Tian-jiao, WANG Qing, SONG Feng-rui, LIU Zhong-ying, LIU Zhi-qiang*,...

2011, 27(3):  380-384. 

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In vitro models of human colon carcinoma cell line(Caco-2 cell monolayer) and human intestinal bacteria were used to investigate the intestinal transport and biotransformation of resibufogenin and cinobufagin in Chan Su by HPLC/APCI-MSn. The experimental results of Caco-2 cell monolayer demonstrate that the apparent permeability coefficients(Papp) of resibufogenin and cinobufagin are higher than 10–6 cm/s, which indicates that both resibufogenin and cinobufagin have a good absorption in the small intestine. And the biotransformation result of human intestinal bacteria shows that resibufogenin has been transformed to 3-epiresibufogenin and cinobufagin has been transformed to 3-epicinobufagin, deacetylcinobufagin and 3-epideacetycinobufagin, respectively.



Determination of Quality Properties of Soy Sauce by Support Vector Regression Coupled with SW-NIR Spectroscopy

LIU Tong, BAO Chun-fang and REN Yu-lin*

2011, 27(3):  385-391. 

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The modern near-infrared(NIR) spectroscopy analysis is a simple, efficient and nondestructive technique, which has been used in chemical analysis in diverse fields. Shortwave NIR spectroscopy is also a rapid, flexible, and cost-effective method to control product quality in food industry. The method of support vector regression coupled with shortwave NIR spectroscopy was explored for the nondestructive quantitative analysis of the important quality parameters of soy sauce, including amino nitrogen content, total acid content, salt content and color ratio. In this study, the support vector regression(SVR) models based on subtractive spectra and positive spectra were found and compared, the results show that the subtractive spectrum was more excellent than the positive spectrum. Meanwhile, R and RSE were determined, respectively, by means of original spectra and pretreated spectra[standard normal variate (SNV), first-derivative and second-derivative], and the corresponding models were successfully established. The best prediction was achieved by a support vector regression model of the first derivative transformed dataset. In addition, the result obtained by the proposed method was compared with that of Partial Least Squares(PLS), which showed that the generalization performance of the classifier based on SVR was much better than that of PLS. The results demonstrate that shortwave NIR spectroscopy combined with SVR is promising for the quality control of soy sauce.



Isolation and Purification of Unstable Iridoid Glucosides from Traditional Chinese Medicine by Preparative High Performance Liquid Chromatography Coupled with Solid-phase Extraction

LI Cun-man, XIAO Yuan-sheng, XUE Xing-ya, FENG Jia-tao, ZHANG Xiu-li*,...

2011, 27(3):  392-396. 

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An efficient preparative method was successfully developed for isolation and purification of unstable components from medicinal plant extracts, using a combined method of preparative high performance liquid chromatography(HPLC) and solid-phase extraction(SPE). The aim of this study was to obtain an effective method with high preparative efficiency and importantly to avoid the transformation of unstable compounds. The preparative HPLC system was based on an LC/MS controlled four-channel autopurification system. The SPE method was performed with a C18 packing material to trap the target compounds and to remove the acidic additive derived from the mobile phase. Using this method, the unstable iridoid glucosides(IGs) as model compounds were successfully isolated and purified from the extract of Hedyotis diffusa Willd. Six IGs(including one new minor IG) and one nucleotide compound were simultaneously obtained, each with a purity of 91% as determined by HPLC. The structures of the isolated compounds were identified by UPLC/Q-TOF MS, UV, 1D and/or 2D NMR. It was demonstrated that the combination of preparative HPLC with SPE is a versatile tool for preparative purification of unstable compounds from complex natural products.



Effects of Simulated Acid Rain on Main Nutritional Indicators of Three Leafy Vegetables

MENG He, DONG De-ming, WANG Ju, YANG Kai-ning, TIAN Lei, SUN Wei and FANG Chun-sheng*

2011, 27(3):  397-401. 

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The purpose of this paper was to identify content changes in the main nutritional indicators of three common leafy vegetables, and to provide a theoretical basis for the protection of leafy vegetables from acid rain. The experiment investigated the effects of simulated acid rain on four main nutritional indicators, including soluble sugar, total free amino acid, soluble protein and vitamin C during the application of simulated acid rain(SAR) in pakchoi(Brassica rapa chinensis), rape(Brassica campestris L.) and lettuce(Lactuca sativa Linn. var. ramosa Hort). The vegetables were respectively exposed to SAR of pH=7.0, 5.6, 5.0, 4.0, 3.0 and a control level of pH=6.5. The concentrations of the four main nutritional indicators were determined at harvest. The results show that nutritional quality of the three leafy vegetable species decreased with the declining of pH values of SAR. The higher the acidity of SAR was, the more significant the inhibitions were. Nutritional quality of lettuce was the most affected by simulated acid rain, followed by pakchoi and rape. The change range of soluble protein content was higher than those of the other three indicators’ contents, which indicates that soluble protein is most sensitive to simulated acid rain.



Adsorption Behavior and Mechanisms of Surfactants by Farmland Soils in Northeast China

CHEN Wei-wei, KANG Chun-li, WANG Ting-ting, LI Yue-ming, ZHANG Ying-xin, WEN Xin and GUO Ping*

2011, 27(3):  402-406. 

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The adsorption of two nonionic surfactants polyethylene glycol tert-octylphenyl ether Triton X-100 (TX-100), polyoxyethylene lauryl ether(Brij35) and an anionic surfactant sodium dodecyl benzene sulfonate(SDBS) by two soils(S1, S2) of different natures and their respective organic-matter-extracted samples(S3, S4) were investigated. These adsorption isotherms show different adsorption stages of different types of surfactants by soils. The data fitted Langmuir equation very well. The adsorption maximum capacity(Q0) indicates that TX-100 and SDBS were in the sequence of S3>S4>S1>S2 in adsorption, however, Brij35 was in the sequence of S4>S3>S1>S2 in adsorption. And the adsorption amounts of the different surfactants by soils followed the order of TX-100>Brij35>SDBS. Meanwhile, the adsorption of the nonionic surfactants TX-100 and Brij35 decreased with the increase of their ethylene oxide(EO) numbers. The results indicate that both soil organic matter and mineral played important roles in the adsorption of surfactants, and the adsorption of the surfactants by soils was affected by the physicochemical properties and structures of the soils and surfactants, especially the mineral type and content of soil.



Preparation of Bio-beads and Their Atrazine Degradation Characteristics

BI Hai-tao, ZHANG Lan-ying, LIU Na* and ZHU Bo-lin

2011, 27(3):  407-412. 

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Screened atrazine-mineralizing bacterium―Pseudomonas W4 was embedded inside an improved PVA- H3BO3 embedment matrix to make bio-beads to degrade atrazine. The atrazine degradation characteristics were studied. The preparation procedure of bio-beads was as follows: (1) preparing a mixture of 100, 12.5, 10, 1.5 and 1 g/L PVA, bentonite(Ca), activated carbon powder, sodium alginate and centrifuged Pseudomonas W4 bacterium, respectively; (2) the mixture was dropped into a gently stirred cross linker solution(pH=6.7) and cured at 10 °C for 24 h. The optimal atrazine degradation conditions by bio-beads were as follows: pH=7, the auxiliary carbon source was glucose, and the concentration of glucose was greater than 325 mg/L. The bio-beads demonstrated stronger tolerance ability than the free microorganism to the increase of PCBs, hydrogen ion and hydroxide ion. SEM images show the uniform distribution of the microorganism inside bio-beads and the porous cross-linked structure of bio-beads which provides excellent mass transfer capacity.



Effects of PAHs on Biotransformation Enzymatic Activities in Fish

LU Guang-hua, CHEN Wei*, LI Ying and ZHU Zhi

2011, 27(3):  413-416. 

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Biotransformation and detoxification responses to the exposure to five polycyclic aromatic hydrocarbons were investigated in crucian(Carassius auratus). Juvenile crucian were treated with a single intraperitoneal injection of each compound at dosages of 0.1, 1.0, 2.0, 5.0 and 8.0(or 10.0) mg/kg and sacrificed 15 d later to determine 7-ethoxyresorufin-O-deethylase(EROD) and glutathione S-transferases(GST) activities in gill S9 fractions. EROD activity is significantly increased by benzo(b)fluoranthene and indeno(1,2,3-cd)pyrene at all the doses. High dosages of PAHs induced GST activity and the inducing ability of them increased in the following order: fluorene<      fluoranthene<indeno(1,2,3-cd)pyrene<benzo(g,h,i)perylene<benzo(b)fluoranthene. In all the cases, dose dependence appeared to exist. The gill EROD and GST in Carassius auratus are useful biomarkers to estimate sub-acute toxicity of both polycyclic aromatic hydrocarbons(PAHs) and PAHs-like compounds.



Copper(I)-catalyzed Synthesis of Aryl, Heteroaryl and Vinyl Sulfides in Aqueous Two-phase System

WANG Li-jin, YUAN Yan-qin and GUO Sheng-rong*

2011, 27(3):  417-421. 

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A fast and convenient C―S bond formation reaction was achieved catalyzed by CuI/L-proline in aqueous two-phase system providing a simple method for synthesis of aryl sulfides in good yields in short time.



Synthesis and Crystal Structure of (3,6-Dichloro-2-nitrophenyl)(3-nitrophenyl)methanone

BAI Fang, GAO Guo-wei, WANG Yang and MEN Jian*

2011, 27(3):  422-425. 

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Novel compounds, (3,6-dichloro-2-nitrophenyl)(3-nitrophenyl)methanone(2), (2-amino-3,6-dichloro- phenyl)(3-aminophenyl)methanone(3) and 1-[3-(2-amino-3,6-dichlorobenzoyl)phenyl]-1H-pyrrole-2,5-dione(4), were synthesized from the initial compound 2,5-dichlorobenzophenone(1) and characterized by 1H NMR, 13C NMR, IR, mass spectrum and element analysis, respectively. The single crystal of compound 2 was obtained and determined by X-ray diffraction analysis. The single crystal data illustrates that it belongs to the monoclinic system, space group P21/c with a=0.7587(4) nm, b=2.4724(4) nm, c=0.8081(3) nm, α=90°, β=112.85(2)°, γ=90?, V=1.3970(9) nm3, Z=4, Dc=1.622 g/cm3, Mr(C13H6Cl2N2O5)=341.10, ?(Mo Kα)=0.49 mm-1, F(000)=688, the final R=0.048 and wR=0.144 for 1665 observed reflections with I>2σ(I). The title molecule forms a “T” type crystal structure and the dihedral angel of the two phenyl rings is 65.0(1)°.



Experimental Researches on Milled Wood Lignin Pyrolysis Based on Analysis of Bio-oil

GUO Xiu-juan, WANG Shu-rong*, WANG Kai-ge and LUO Zhong-yang

2011, 27(3):  426-430. 

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The structure of milled wood lignin(MWL), isolated via the Bj?rkman procedure, was studied by means of 1H NMR spectroscopy and Fourier transform infrared spectroscopy, and then its pyrolytic product distribution was investigated on a pyrolysis device. MWL obtained from Manchurian Ash(MA) contained more methoxyl and free phenolic hydroxyl groups per C9 unit than MWL from Mongolian Pine(MP) due to the existence of both guaiacyl and syringyl units, which have a major influence on the pyrolysis behavior of lignin. The results of pyrolysis show that MWL from MA generated a higher yield of bio-oil, mainly composed of phenols, guaiacols, syringols and catechols, and a less yield of char, in addition to the gaseous products CO, CO2, methane and methanol, compared with MWL from MP. Guaiacol and syringol were the typical products from G-lignin and S-lignin, probably attributed to the easier cleavage of the aryl-alkyl linkage in the side chain compared with the C―OCH3 bond in the benzene ring. The degradation of MWL from MP was dominated by the demethylation reaction and the cleavage of aliphatic ―CH2OH at the γ-position, followed by the cracking of the Cα―Cβ and C4―Cα bonds.



Design and Synthesis of 3-(1-Phenylethyl)thiazolidine-2-thione Derivatives with Potential Biological Activities

LI Hong-xin, CHEN Xiao-tao and XU Liang-zhong*

2011, 27(3):  431-434. 

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A series of novel neonicotinoids derivatives 4a―4p was designed and synthesized by introducing the ethylbenzene group into the thiazole ring, their structures were confirmed by IR, 1H NMR and elemental analysis. The crystal structure of compound 4j has been determined by X-ray diffraction analysis.



Novel Synthesis of 2-Amino-3-ethoxycarbonyl Benzopyrans with Onium Salt as Soluble Support

ZHANG Li, LU Cui-fen, YANG Gui-chun and CHEN Zu-xing*

2011, 27(3):  435-440. 

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Task specific onium salt has been presented as soluble support in the synthesis of benzopyrans in this  paper. This method allows for results by far superior to those reported other soluble supports and allows for very easy purifications of reaction products.



Construction, Expression and Characterization of a Chimeric Protein Targeting Carcinoembryonic Antigen in Lung Cancer

LI Yang, HUA Shu-cheng, MA Cheng-yuan, YU Zhen-xiang, XU Li-jun, LI Dan, ...

2011, 27(3):  441-444. 

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The carcinoembryonic antigen(CEA) is an oncofetal glycoprotein known as an important clinical tumor marker and is overexpressed in several types of tumors, including colorectal and lung carcinomas. We constructed a chimeric protein that exhibits both specific binding and immune stimulating activities, by fusing staphylococcal  enterotoxin A(SEA) to the C-terminus of an anti-CEA single-chain disulfide-stabilized Fv(scdsFv) antibody     (single-chain-C-terminus/SEA, SC-C/SEA). The SC-C/SEA protein was expressed in Escherichia coli(E. coli), refolded, and purified on an immobilized Ni2+ affinity chromatography column. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis(SDS-PAGE) and  Western blot analysis reveal that the target protein was expressed sufficiently. We used immunofluorescence assays to demonstrate that SC-C/SEA could bind specifically to human lung carcinoma cells(A549), but almost human uterine cervix cells(HeLa). We also used the L-lactate dehydrogenase(LDH) release assay to show that SC-C/SEA elicits a strong A549 tumor-specific cytotoxic T lymphocyte(CTL) response in vitro. The results suggest that SC-C/SEA shows specific activity against CEA-positive cells and has potential application in CEA-targeted cancer immunotherapy.



Lentivirus-mediated RNA Interference and Over-expression of CDK2AP1 CDNA Regulate CDK2AP1 Expression in Human Lung Cancer A549 Cells

GAO Nan, ZHANG Xing-yi, JIANG Rui, WANG Guan, LI Jin-dong, JIN Cheng-yan and SUN Mei*

2011, 27(3):  445-449. 

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Cyclin-dependent kinase 2-associated protein 1(CDK2AP1), a cell growth inhibitory factor, is abnormally expressed in cancer cells, and might be implicated in the development of lung cancer. However, no studies on the function of CDK2AP1 in human lung cancer have been yet reported. In this study, overexpressing lentiviral vectors containing full-length CDK2AP1 cDNA and CDK2AP1 shRNA(short hairpin RNA) were constructed. Our results show that infecting A549 cells with lentivirus containing CDK2AP1 shRNA or full-length CDK2AP1 cDNA results in significantly down- or up-regulated the expression of CDK2AP1, respectively, thereby providing reliable tools for studying the function of CDK2AP1 in pulmonary carcinogenesis. Our data of MTT assay and flowcytometric analysis demonstrate that CDK2AP1 plays an important role in the proliferation/growth and cell cycling of A549 cells in vitro, and further investigation into its underlying mechanism of pulmonary carcinogenesis is needed.



Structure Characteristic and Catalase Activity of Vitreoscilla Hemoglobin Bound with Membrane

ZHAO Hai-feng, WU Lei, LU Ming, HU Yu-lin, HAN Xiao and LI Zheng-qiang*

2011, 27(3):  450-454. 

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Lipid-bound [VHb(406)] and lipid-free [VHb(402)] wide type Vitreoscilla hemoglobin were separated from E. coli BL21(DE3). The RZ is 3.30 for [VHb(406)] and 3.15 for [VHb(402)], respectively. VHb(406) shows a characteristic absorption band at 626 nm, while VHb(402) shows one at 644 nm, and it has more α-helix than VHb(402). Data of Raman spectra experiment shows under the excitation wavelength 488 nm, υ4 vibration of both VHb(402) and VHb(406) had a pure and strong signal at 1375 cm-1, which proves that iron porphyrin of both the samples is at their trivalence oxidation state. And no matter lipid binds VHb or not, the vinyl of porphyrin is at cis state. The catalase activity of Vitreoscilla hemoglobin was explored with L-dopa and H2O2 as substrates. The results indicate that VHb(406) has more catalase activity than VHb(402), VHb is a cell’s oxygen modulator and its catalase ability is modulated by the membrane.



Activity of T Cells Stimulated by Hemagglutinin-neuraminidase of Newcastle Disease Virus in vivo

PIAO Bing-guo, LI Xiao, SUN Li-li, KAN Shi-fu, LIU Lei, HUANG Hai-yan, ...

2011, 27(3):  455-460. 

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To investigate the stimulated activity of T cells and the anti-tumor properties of hemagglutinin-neurami- nidase(HN) of Newcastle disease virus(NDV) strain Changchun(NDVcc), the expression of HN gene in hepatoma cells(human HepG-2 and mouse H22 cells) infected with the recombinant adenovirus(Ad-HN) was identified by Western blot analysis and flow cytometry. Sialidase activity of NDVcc HN expressed by Ad-HN was assayed by the periodate-resorcinol method. The in vivo anti-tumor effects of NDVcc HN were evaluated in the H22 solid tumor model. Regional lymph nodes of the mouse model treated with Ad-HN were removed to harvest T lymphocytes and evaluating the specific cytotoxicity of cytotoxic T lymphocyte(CTL) and natural killer(NK) cells by an L-lactate dehydrogenase(LDH) assay, in the mean time, the secretion of cytokines was analyzed by enzyme linked immunosorbent assays(ELISA). The results show that NDVcc HN was effectively expressed by Ad-HN in HepG-2 and H22 cells. The sialidase activity assay showed that Ad-HN significantly reduced sialic acid level of the hepatoma cells compared with the cells infected the empty adenovirus vector(Ad-mock). When treated with Ad-HN, the growth of subcutaneous H22 primary tumors in C57BL/6 mice was suppressed, and the mean mice survival increased. In addition, the treatment of Ad-HN elicited strong NK and CTL responses, and high levels of Th1 cytokines, such as IL-2 and IFN-γ. In conclusion, NDVcc HN effectively elicits T cell-mediate anti-tumor cytotoxicity via sialidase activity and may be a novel strategy for cancer immunotherapy.



Identification of Herbal Compound Imperatorin with Adverse Effects on ANO1 and CFTR Chloride Channels

HAO Feng, YI Fei, ZHANG Di, NING Yan, SU Wei-heng, FENG Xue-HAO Feng, YI Fei, ZHANG Di, NING Yan, SU Wei-heng, FENG Xue-chao, YANG Hon, ...chao1, YANG Hong2 and MA Tong-hui1*

2011, 27(3):  461-463. 

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Calcium-activated chloride channels(CaCCs) are the crucial regulators of transepithelial fluid secretion, smooth muscle contraction and sensory transduction. Recently, compelling evidence has indicated that TMEM16A(ANO1 or anoctamin-1) is a bona fide calcium-acvtivated chloride channel. A few small molecule CaCCs regulators are available for functional and therapeutic studies. We screened 126 natural compounds from Chinese herbs. Screening was performed with an iodide in?ux assay in Fischer rat thyroid epithelial cells to coexpress ANO1 and an iodide-sensitive ?uorescent indicator(EYFP-H148Q/I152L). Imperatorin, a coumarin compound, was identified to inhibit ANO1-mediated chloride transport activated by multiple calcium-elevating agonists. The inhibitory  effect is dose-dependent with IC50 ~14.63 μmol/L. Interestingly, imperatorin activated CFTR chloride channel with EC50 ~35.52 μmol/L. The adverse effects of imperatorin on CaCC and CFTR chloride channels will make it useful in pharmacological dissection of chloride transport in airway and intestinal epithelium. Further studies are required to evaluate the therapeutic effects of imperatorin on hypertension, asthma and certain tumors.



Expression of SOCS-3 and Its Methylation in Renal Cancer

YU Jing, ZHAO Li-chun, YAO Song-mei, HE Cheng-yan, LI Hong-jun* and KONG Xiang-bo

2011, 27(3):  464-467. 

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The expression level of suppressor of cytokine signaling-3(SOCS-3) in human renal carcinoma and its methylation state were investigated. Reverse transcription-polymerase chain reaction(RT-PCR), immuocytochemistry, immunohistochemistry and Western blot were used to detect the expression level of SOCS-3, and the methylation of SOCS gene was investigated by methylation specific PCR in the tissues of 15 cases of renal carcinoma. Compared to those of the normal renal cell line and specimens , the expression level of SOCS-3 in renal carcinoma was significantly lower or can’t be detected(P<0.01). And the methylation of SOCS-3 gene in the tissue of renal carcinoma was significantly higher. The expression of SOCS-3 gene is significantly lower in renal carcinoma and the high methylation of the promoter island of SOCS-3 gene is associated with the lower expression of SOCS-3 gene. It may be one of main mechanisms for the development and progress of renal carcinoma.



Toxicity of Naphthalene on Caenorhabditis elegans

ZHANG Shu-hua, XU Jing-bo*, LIU Cheng-bai, LI Qiao, GUAN Shu-wen, ...

2011, 27(3):  468-473. 

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Naphthalene is a common environmental contaminant substance. The toxic effects of naphthalene on Caenorhabditis elegans were investigated at the molecular, biochemical and physiological levels. To assess the molecular-level effect, stress-related gene expression was investigated such as those of hsp-16.1, sod-3, ctl-2, cep-1, cyp35a2, ugt-44, gst-1 and dhs-28. Cell apoptosis was assessed at the biochemical level. Life span, locomotion behaviors and brood size were investigated at the physiological level. The results indicate that naphthalene exposure could not only induce the expression of stress-related genes such as hsp16.1, sod-3, ctl-2 and cep-1 but also reduce the life span of Caenorhabditis elegans. At the same time, naphthalene exposure could result in cell apoptosis and interfere in the locomotion behaviors of Caenorhabditis elegans. These data suggest that naphthalene has multiple toxicity on Caenorhabditis elegans.



Expression and Characterization of the Intracellular Part of Receptor Protein Tyrosine Phosphatase PTPRU

WANG Shao-feng, HAN Jia-yu, FU Xue-qi* and ZHAO Zhi-zhuang Joe*

2011, 27(3):  474-477. 

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PTPRU is an MAM domain-containing receptor-like protein tyrosine phosphatase. Previous studies have demonstrated an important role of the enzyme in the maintenance of epithelial integrity and in the regulation of the Wnt/?-catenin signaling pathway. To better understand the function of PTPRU, we cloned and expressed the intracellular portion of PTPRU as a GST fusion protein in E. coli cells. We purified the protein to homogeneity and used it to immunize mice for antibody production. The resultant antibody specifically recognized PTPRU over-expressed in the cell line. Western blot analyses demonstrated the partition of truncated forms of PTPRU containing the cadherin-like domain in the Triton X-100-insoluble fraction, and immunofluorescent cell staining revealed the localization of these proteins in punctate intracellular structures. Our data suggest that the cadherin-like domain of PTPRU has a major role in determining its intracellular localization.



Electrochemical Performance of Solid Polymer Electrolyte PEO20-LiTf-Urea1.5

ZHANG Ding, YAN Hui, ZHANG Huan and QI Lu*

2011, 27(3):  478-481. 

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A new solid polymer electrolyte PEO20-LiTf-Urea1.5 was prepared by solution casting technique. The energy of frontier orbitals for the components of the electrolyte was predicted by quantum chemistry calculations, and TG stability and electrochemical features were measured. Urea exhibited a lower HOMO energy than PEO, implying its enhanced stability against electrochemical oxidation. Experimentally addition of urea increases the ionic conductivity, which guarantees conductivity requirement for lithium ion batteries. It also results in significant improved electrochemical stability with good thermal stability. Favorable lithium stripping/plating performance is yielded, and it confirms the good stability of the solid electrolyte interphase for the PEO20-LiTf-Urea1.5 system.



Phase Equilibrium of Quaternary System Cd2+//Cl–, SO42–, NO3–-H2O at 298 K

HUANG Yi*, ZOU Fang, NI Shi-jun and SANG Shi-hua

2011, 27(3):  482-485. 

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Solid-liquid equilibrium of quaternary system Cd2+//Cl–, SO42–, NO3–-H2O at 298 K was studied by means of an isothermal solution saturation method. Experimental results indicate that there are three univariant curves BE, AE and CE, one invariant point E and three crystallization fields in the quaternary system. The quaternary system belongs to a simple type, and there are no double salts or solid solution existing. The crystallization zones of equilibrium solid phases are CdCl2·5/2H2O(AEB field), 3CdSO4·8H2O(AEC field) and Cd(NO3)2·4H2O(BEC field), respectively. The composition of the invariant point is CdCl2, Cd(NO3)2, CdSO4 and H2O and the contents of which are 17.02%, 45.50%, 4.52% and 32.96%, respectively. The physico-chemical properties of solution in the quaternary system show regular changes along with the increased cadmium concentration. The results indicate that Cd(NO3)2 possessed the highest solubility among those three salts, which means a strong transfer of Cd ion and a high pollution risk of soil environment. And the solubility of CdSO4 would be restrained as the salts existing together.



Methanol Oxidation over TiO2-modified Multi-walled Carbon Nanotubes Supported Pt-Mo Electrocatalyst

WANG Xiu-yu, JIANG Yuan-sheng, ZHU Hong and ZHANG Jing-chang*

2011, 27(3):  486-489. 

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In order to develop a novel and high-performance catalytic material for direct methanol fuel cells(DMFC), molybdenum oxide as a co-catalyst with Pt on multi-walled carbon nanotubes which were modified by titanium dioxide(denoted as CNTs@TiO2) was investigated. The physicochemical characterizations of the catalysts were carried out via X-ray diffraction(XRD), transmission electron microscopy(TEM) and X-ray photoelectron spectroscopy(XPS). Cyclic voltammetry(CV) showed that the CO-tolerance performance increased in the sequence of Pt/CNTs< Pt/CNTs@TiO2<Pt-Mo/CNTs@TiO2. The improved CO-tolerance performance of the Pt-Mo/CNTs@TiO2 catalyst can be attributed to the combined beneficial effects of highly dispersed Pt nanoparticles on the CNTs, the existence of oxygen holes in the MoO3 layer structure and the oxidation capability of TiO2.



Structure of MgSO4 in Concentrated Aqueous Solutions by X-Ray Diffraction

CAO Ling-di, FANG Yan* and FANG Chun-hui*

2011, 27(3):  490-495. 

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Detailed time-and-space-averaged structure of MgSO4 in the concentrated aqueous solutions was investigated via X-ray diffraction with an X’pert Pro θ-θ diffractometer at 298 K, yielding structural function and radial distribution function(RDF). The developed KURVLR program was employed for the theoretical investigation in consideration of the ionic hydration and ion association. Multi-peaks Gaussian fitting method was applied to deconvolving the overlapping bands of Differential radial distribution function(DRDF). The calculation of the geometric model shows that octahedrally six-coordinated Mg(H2O)62+, with an Mg2+···OW bond length of 0.201 nm dominates in the solutions. There exists contact ion-pair(CIP) in the more concentrated solution(1:18, H2O/salt molar ratio) with a coordination number of 0.8 and a characteristic Mg···S distance of 0.340 nm. The result indicates the hydrated SO42– ion happens in the solution. The S···OW bond distance was determined to be 0.382 nm with a coordination number of 13. The fraction of CIP increases significantly with the increasing concentration. The symmetry of the hydration structure of sulfate ion is lowered by forming complex with magnesium ion.



Facile Synthesis of Gold Nanoparticle-loaded Carbon Nanofiber Composites and Their Electrocatalytic Activity Towards Dopamine, Ascorbic Acid and Uric Acid

TENG Hong, LIU Yang and YOU Tian-yan*

2011, 27(3):  496-499. 

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A facile approach for the synthesis of gold nanoparticle-loaded carbon nanofiber(Au/CNF) composites was developed. When applied to electrochemistry, these composites showed attractive performances such as high conductivity and facile electron transfer kinetics. Under physiological conditions, the Au/CNF composite modified electrode exhibits highly electrocatalytic activity for the oxidation of dopamine, ascorbic acid and uric acid. Owing to the good selectivity for the simultaneous detection of these three species, the novel composites are promising for the development of effective electrochemical biosensors.



Preparation and UV-light Absorption Property of Oleic Acid Surface Modified ZnO Nanoparticles

KANG Jong-hun, GUO Yu-peng, CHEN Yue and WANG Zi-chen*

2011, 27(3):  500-502. 

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Syntheses of zince oxide(ZnO) nanoparticles by direct precipitation and surface modification with oleic acid were reported. ZnO nanoparticles were characterized via X-ray diffractometry(XRD), transmission electron  microscopy(TEM), infrared spectroscopy(IR) and UV-Vis spectroscopy. The prepared ZnO nanoparticles were nearly spherical and highly crystalline with an average size of 29 nm. In addition, high UV-light absorption properties of oleic acid surface modified ZnO nanoparticles were successfully obtained for a dispersion of ZnO nanoparticles in ethanol.



Hydroxylation of Benzene to Phenol via Hydrogen Peroxide in Hydrophilic Triethylammonium Acetate Ionic Liquid

HU Xiao-ke, ZHU Liang-fang, GUO Bin, LIU Qiu-yuan, LI Gui-ying and HU Chang-wei*

2011, 27(3):  503-507. 

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A new Fenton-like system in a medium of hydrophilic triethylammonium type of ionic liquid(IL) was used for the hydroxylation of benzene to phenol. The triethylammonium acetate([Et3NH][CH3COO]) IL exhibited retardation performance for the decomposition of H2O2 and protection performance for the further oxidation of phenol, thus the yield and selectivity to phenol were promoted greatly. The acidity of the system was proved to be an important factor for the selectivity to phenol. The utilization of H2O2 and the selectivity to phenol, as well as the Turnover number(TON) of the catalyst were effectively enhanced by a benzene-[Et3NH][CH3COO] bi-phase system. The catalyst with [Et3NH][CH3COO] IL was recycled with stable catalytic performance.



Ionization and Fragmentation of Butanone Clusters Irradiated by Photons at 355 and 118 nm

SUN Chang-kai, HU Zhan, YANG Xue, JIN Ming-xing, HU Wen-cheng and DING Da-jun*

2011, 27(3):  508-511. 

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Time-of-flight(TOF) mass spectra of molecular butanone clusters were measured under the irradiation of photons at 355 and 118 nm. Butanone molecular parent ion and several series of butanone cluster fragments such as (CH3COC2H5)nH+, (CH3COC2H5)nC2H5+, (CH3COC2H5)nCH3CO+ and (CH3COC2H5)nC2H5CO+ were observed. Odd-even variation pattern in the intensity of (CH3COC2H5)nCH3CO+ is obvious from n=4 to 8. A connection is established between the fragment clusters (CH3COC2H5)nCH3CO+ and the neutral clusters (CH3COC2H5)n+1 based on the consideration of butanone cluster dissociation mainly by losing a radical C2H5?. The stability variation of the neutral clusters calculated via the HF-B3LYP method based on DFT is in agreement with the observed phenomena experimentally, indicating (CH3COC2H5)n+1(n+1=5,7) with a ring structure are with higher stability over the adjacent even-number clusters.



Lithium Salt of NH2-substituted Graphene Nanoribbon with Twofold Donor-acceptor Framework: Large Nonlinear Optical Property

ZHOU Zhong-jun, LI Zhi-ru*, HUANG Xu-ri* and SUN Chia-chung

2011, 27(3):  512-515. 

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Based on graphene, a new class of second-order nonlinear optical(NLO) material, the lithium salt of NH2-substituted graphene nanoribbon with the twofold donor(D)/acceptor(A) mode, was reported. Eight stable 2Li-2NH2-GNR lithium salts, especially cis lithium salts, display considerably large β0 values. The combination of NH2-substituting and cis Li-doping makes β0 greatly increased from 0(GNR) to 1.2×105―2.9×105 a.u.(cis-2Li- 2NH2-GNRs). Our largest β0 value(2.9×105 a.u.) for cis-2Li-1,3-2NH2-AGNR is comparable to the record value of 1.7×105 a.u. for a long donor-acceptor polyene.



Preparation and Characterization of Ordered Ladder Like Polyphenylsilsesquioxane via Two-step Sol-gel Method

FENG Yu-zhong, QI Sheng-li, LIU Jing-jing, WU Zhan-peng, YANG Xiao-ping, JIN Ri-guang and WU De-zhen*

2011, 27(3):  516-519. 

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Soluble and ordered ladder like polyphenylsilsesquioxane was synthesized by a two-step sol-gel method including hydrolysis and polycondensation. The procedure was monitored by Fourier transform infrared spectroscopy and the presence of the ladder like structure was confirmed by X-ray techniques. 29Si NMR analysis shows a very narrow half peak width(δ<4) at δ –78.866 of the main chain unit C6H5SiO3/2 of polyphenylsilsesquioxane, indicating that the polyphenylsilsesquioxane has ordered ladder like structures rather than the branched ones. The relationship between molecular weight and the time of polycondensation was also discussed.



Allyl-containing Poly(aryl ether sulfone): Synthesis and Crosslinking

YU Yun-wu, XING Yan, GUO Mei-mei, LIU Bai-jun* and JIANG Zhen-hua

2011, 27(3):  520-523. 

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A novel type of crosslinkable poly(aryl ether sulfone)(PAES) bearing an allyl pendant(PES-OAllyl) was synthesized by a grafting reaction of hydrophenyl-containing PAES(PES-OH) and allyl bromide. PES-OH was prepared by a demethylation reaction of a methoxyphenylated PAES(PES-OCH3) in the presence of pyridine/hydrochlo- ride. The PES-OCH3 was synthesized by an aromatic nucleophilic substitution of bis(4-chlorophenyl)sulfone and (p-methoxy)phenylhydroquinone. Both DSC and solubility investigation were used to study the crosslinking behavior of PES-OAllyl. After heat treatment, the glass transition temperature(Tg) value of PES-OAllyl sharply increased from 165 °C to 227 °C. Meanwhile, PES-OAllyl changed from a soluble polymer to an insoluble thermoset. In addition, TGA(thermogravimetric analysis) result suggests that the thermal stability of the crosslinked product was improved. All the data prove that the crosslinked PES-OAllyl could be a potential solvent-resistance high-performance material.



Sandwich Structure-like Meshes Fabricated via Electrospinning for Controllable Release of Zoledronic Acid

LU Jian, LIU Jian-guo*, SONG Xiao-feng, CHEN Xue-si and WU Xiao-dong

2011, 27(3):  524-527. 

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Novel sandwich structure-like nano?ber multilayered meshes were fabricated via electrospinning. The purpose of the present work was to control zoledronic acid release via the novel structure of sandwich structure-like meshes. The in vitro release experiments reveal that the drug release speed and initial burst release were controllable by adjusting the thicknesses of electrospun barrier mesh and drug-loaded mesh. Compared with those of other drug delivery systems, the main advantages of the sandwich structure-like fiber meshes are facile preparation conditions and the generality for hydrophobic and hydrophilic pharmaceuticals.



Research Note

Electrochemical Cycled Structure of MnV2O6 Nanoribbons Synthesized via Hydrothermal Route

HU Fang, ZHANG Chun-hua, ZHANG Song, MING Xing, CHEN Gang, WEI Ying-jin, ...

2011, 27(3):  528-530. 

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MnV2O6 nanoribbons were prepared by a simple hydrothermal route. Scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM) confirmed these MnV2O6 single crystalline nanoribbons fabricated along the <200> axis. Electrochemical tests in rechargeable lithium batteries showed that MnV2O6 nanoribbons exhibited a high first discharge capacity of 810 mAhg-1. The crystal structure and local structure of the material during the cycles were studied by X-ray diffraction and Infrared spectrum. The loss of long-range ordering and short-range ordering could be regarded as the important factors for the capacity fading of MnV2O6 as an anode material for Li-ion batteries.