Table of Content

25 September 2009, Volume 25 Issue 5

Previous Issue    Next Issue

Content

Content of Chemical Research in Chinese Universities Vol.25 No.5(2009)

2009, 25(5):  0. 

Abstract ( )   PDF (1001KB) ( )  

Related Articles | Metrics

Articles

Controlled Growth Morphology of Porous Nanocrystal Iron Oxide by Electrodeposition

LI Li and SHI Ke-ying*

2009, 25(5):  595-599. 

Abstract ( )   PDF (668KB) ( )  

References | Related Articles | Metrics

Fe(II) was deposited into the bottom of the mesopores of highly ordered large caged cubic mesoporous silica by electrodeposition. And the deposited Fe mesoporous silica thin film was treated by 1%―4% HF to remove the SiO₂ template and then calcined. It was found that nanowire bundles, dendritic plates of porous iron oxide, dense parallel backbones of porous iron oxide were obtained at –1.4― –1.6 V and 0.08―0.1 mol/L electrolyte concentration after calcinations; the dendritic pattern of porous iron oxide film templated by the SBA-16 film was obtained in macrostructure at a higher absolute value of cathode potential(–1.7― –1.8 V) and a lower electrolyte concentration(0.02―0.05 mol/L), the dendritic pattern of porous iron oxide film could copy the microstructure of SBA-16 film; Fe(II) nanowires grew and formed in one dimension(1D) and two-dimension(2D) electrocrystallization at a potential of –1.6― –1.7 V and an electrolyte concentration of 0.05 mol/L, and the shape of the 1D or 2D crystalline iron oxide nanowires calcined was similar to the original shape of the SBA-16 channels. The desired morphology and size of porous nanocrystal iron oxide can be obtained by adjusting the applied potential value and electrolyte concentration, and all kinds of morphologies of porous nanostructure crystal iron oxide can be prepared.

In situ Preparation of Tri-Fe(III) and Bi-Cu(II) Clusters from Benzoyl Peroxide Reacting with Metal Powders

YANG Jun-wei, ZHANG Jing, TONG Shan-ling*, HUANG Xiao-chun and YAN Yan*

2009, 25(5):  600-605. 

Abstract ( )   PDF (945KB) ( )  

References | Related Articles | Metrics

Three crystal architectures, including one organic compound of benzoyl peroxide(1) and two clusters of tri-iron(III) and bi-cupper(II) with benzoic ligands(2 and 3), were self-assembled by an in situ redox way of benzoyl peroxide oxidants reacting with Mo, Fe and Cu powders, respectively. X-ray crystallographic results show that both the asymmetry tri-iron(III) cluster and the benzoylperoxide crystal architecture(2 and 1) with complicated 3D networks were constructed by intermolecular hydrogen-bonding interactions. Contrarily, the symmetrical bi-copper(II) cluster crystal architecture(3), only with π-π stacking between paralleled phenyl groups and without any intermolecular hydrogen-bonding interactions, only presented an 1D zigzag chain along the a-axis.

Detection of Trace Heavy Metals Ions by Arrays of Titania Nanotubes Annealed in Nitrogen

ZHAO Zhi-man*, XIAO Peng and CAO Guo-zhong

2009, 25(5):  606-609. 

Abstract ( )   PDF (287KB) ( )  

References | Related Articles | Metrics

Redox response of trace heavy metals ions(THMIs) has better performance on highly ordered vertically oriented titania nanotube arrays(TNA) annealed in nitrogen. Experimental data showed that different THMIs possess different reaction peak shapes and charge and discharge capacities. Therefore, the TNA will become an important tool used for environmental protection and facilitating the rapid determination of THMIs. THMIs of 5×10^–4 mol/L concentration were measured at a scan rate of 100 mV/s. The analytical utility of TNA is demonstrated in a neutral 0.5 mol/L Na₂SO₄ solution. The results sufficiently show that titania nanotube arrays electrodes(TNAE) will be used to measure THMIs.

Spectral Characteristics of LiSrBO₃:Tb³⁺ Green Phosphor

LI Pan-lai*, WANG Zhi-jun, YANG Zhi-ping and GUO Qing-lin

2009, 25(5):  610-613. 

Abstract ( )   PDF (225KB) ( )  

References | Related Articles | Metrics

LiSrBO₃:Tb³⁺ green phosphor was synthesized by means of a solid state reaction and its spectral characteristics were studied. The emission spectrum of LiSrBO₃:Tb³⁺ consists of four major bands at 486, 544, 595 and 620 nm under the excitation of near ultraviolet irradiation, which are originated from the ⁵D₄→⁷F₆, ⁵D₄→⁷F₅, ⁵D₄→⁷F₄ and ⁵D₄→⁷F₃ characteristic transitions of Tb³⁺, respectively. Monitored at 544 nm, the excitation spectrum of the phosphor extends from 220 nm to 390 nm, with the excitation peaks centered at 242, 277, 368 and 381 nm, respectively. The effect of Tb³⁺ concentration on the emission intensity of LiSrBO₃:Tb³⁺ was also investigated. The results show that firstly the intensity increases with increasing Tb³⁺ concentration, reaches a maximum value at 3%(molar fraction) Tb³⁺ and then decreases, showing a concentration self-quenching, whose mechanism is proposed as a d-d interaction based on Dexter theory. The emission intensity of LiSrBO₃:Tb³⁺ was enhanced by co-doping Li⁺, Na⁺  and K⁺.

Synthesis, Structure and Properties of Three-dimensional Gd(Ⅲ), Eu(Ⅲ) Coordination Polymers via in situ Decarboxylation

WANG Chuan-sheng, GU Xiao-fu, SUN Ya-guang*, GAO En-jun and ZHANG Wan-zhong

2009, 25(5):  614-619. 

Abstract ( )   PDF (407KB) ( )  

References | Related Articles | Metrics

Two three-dimensional lanthanide(III) coordination polymers with the formula [Ln(PYDC)(NA)(H₂O)]_n [Ln=Gd(1), Eu(2), H2PYDC=pyridine-2,5-bicarboxylic acid, HNA=nicotinic acid] have been hydrothermally synthesized and characterized by elemental analysis, IR, and single crystal X-ray diffraction. The NA came from in situ decarboxylation of the part of PYDC. X-ray single crystal structural analyses reveal that complexes 1 and 2 are isomorphous, they possess the 4³·6³ topology assembled by Gd³⁺/Eu³⁺ and two different multidentate carboxylate ligands. Magnetic measurements show that antiferromagnetic coupling exists between adjacent Gd³⁺ ions in complex 1. The complex 2 exhibits the corresponding characteristic luminescence in the visible region under an excitation at 305 nm.

A Quinoline Derivated Chemosensor for Cu²⁺ Recognition

FAN Cai-ling*, DAI Xing, YANG Wu-min, WANG Xing-feng and YANG Yun-xu*

2009, 25(5):  620-623. 

Abstract ( )   PDF (363KB) ( )  

References | Related Articles | Metrics

A quinoline derivative N-(2-hydroxyl-naphthylmethyl)-N-(quinol-8-yl)amine(2) was synthesized and characterized, which can selectively recognize Cu²⁺ over other metal ions such as Zn²⁺, Cd²⁺, Sn²⁺, Pb²⁺, Hg²⁺, Ni²⁺, Mg²⁺, Cr³⁺, Mn²⁺, Sr²⁺, K⁺, Ca²⁺, Na⁺, Ba²⁺ in acetonitrile/water(volume ratio 99:1). Cu²⁺ induced a new absorption peak at 464 nm in the absorption spectrum(ε=4.66×10² L·mol^–1·cm^–1) and quenched the fluorescence emission of quinoline derivative 2. The binding of quinoline derivative 2 to Cu²⁺ was in 1:1 model and stable constant was estimated to be 2.48×10⁵ L·mol^–1.

High Sensitive Long Period Fiber Grating Sensor for Detection of Nitrite

QIAN Ying*, YU Yong-sen, LI Qiu-shun, WU Si-zhu, ZHAO Kai-jun*, ......

2009, 25(5):  624-627. 

Abstract ( )   PDF (579KB) ( )  

References | Related Articles | Metrics

A high sensitive long period fiber grating(LPFG) sensor for the detection of nitrite is proposed, which is realized by coating multiple poly(sodium 4-styrensulfonate)(PSS) and poly(diallyldimethylammonium) chloride (PDDA) layers on the fiber grating surface. The sensitivity of this LPFG sensor is maximum when the number of assembled layers is 70. Under this condition, a nitrite concentration of 3×10^–3 mol/L, which is lower than the National Food Additive Standard, 4.2×10^–3 mol/L, can be distinguished. The sensitivity is further increased by 30% when nitrite was determined in the sucrose solution with a concentration of 65%, which provides a new solution for the best refraction index approaching matched index of the fiber cladding. Compared with chemical methods, this nitrite detection technology offers some advantages, such as high accuracy, non toxicity, high speed, low cost, without chemical reagent, and is suitable for foodstuff security detection.

Synthesis and Analytical Application of Bis(2-diazoaminobenzothiazoyl)-benzidine to Determination of Mercury Ion by Fluorimetry

JIANG Run-sheng, FENG Feng*, CHEN Ze-zhong, BAI Yun-feng, LIN Sen, ......

2009, 25(5):  628-632. 

Abstract ( )   PDF (293KB) ( )  

References | Related Articles | Metrics

A new fluorescent reagent bis(2-diazoaminobenzothiazoyl)-benzidine(BDABTB) was synthesized by combining benzothiazole with benzidine and triazene reagent. The product was confirmed by elemental analysis, ¹H NMR and FTIR. The excitation and emission wavelengths of BDABTB were 214 and 338 nm in a basic medium, respectively. The fluorescence was quenched by Hg²⁺ selectively and sensitively. The linear range of Hg2+ was 1.0×10^–8―1.0×10^–5 mol/L with a detection limit of 5.0×10^–10 mol/L. It has been used to determine trace Hg²⁺ in water sample with satisfactory results.

Development of Near Infrared Spectroscopy for Rapid Quality Assessment of Red Ginseng

NIE Li-xing*, WANG Gang-li and LIN Rui-chao

2009, 25(5):  633-637. 

Abstract ( )   PDF (187KB) ( )  

References | Related Articles | Metrics

Near infrared spectroscopy(NIRS) was developed as a rapid analysis method for the qualitative and quantitative assessment of the quality of red ginseng. Discriminant analysis(DA) based on principal component analysis and Mahalanobis distance was used to distinguish red ginseng from counterfeits non-destructively. The result shows that the proposed method could distinguish red ginseng from counterfeits correctly and no misclassified sample was found in both training and test sets. The partial least squares(PLS) algorithm was used to predict the sum of ginsenosides Re and Rg1 and the content of ginsenoside Rb1. Two calibration models were developed to correlate NIR spectra with the reference values determined by HPLC method. The correlation coefficient(R), the root mean square error of calibration(RMSEC) and the root mean square error of prediction(RMSEP) were as follows: R=0.9827, RMSEC=0.0163%, RMSEP=0.0250% for the sum of ginsenosides Re and Rg₁; R=0.9869, RMSEC=0.0156%, RMSEP=0.0256% for content of ginsenoside Rb₁. The overall results demonstrate that NIRS coupled with chemometrics could be successfully applied as a rapid, precise and cost-effective method not only to identify the red ginseng from counterfeits but also to determine simultaneously some chemical compositions in red ginseng.

Ce(SO₄)₂-mediated Oxidative Coupling of Primary Aromatic Amines in Water

LU Wen-chao and XI Chan-juan*

2009, 25(5):  638-643. 

Abstract ( )   PDF (356KB) ( )  

References | Related Articles | Metrics

The oxidative coupling of primary aromatic amines was investigated. Ce(SO₄)₂ can mediate the oxidative coupling of primary aromatic amines in water to dimers, trimers and/or tetramers, which depended on the substituents of primary aromatic amines. When 2,6-dimethylaniline or 2,6-diethylaniline was used as substrate, dimer, and tetramer were formed as major products. When 2,6-diisopropylaniline or 2,6-dihaloanilines was used as substrate, dimer, and trimer were formed. The mechanistic aspect was also investigated.

Cytotoxic Activity of Some Novel Dicoumarin Derivatives in vitro

ZHANG Hui, YU Tian-zhi*, ZHAO Yu-ling, FAN Duo-wang, DING Lan and ZHANG Shi-dong

2009, 25(5):  644-647. 

Abstract ( )   PDF (471KB) ( )  

References | Related Articles | Metrics

Some novel dicoumarin derivatives, triethylene-glycol dibenzo[5,6] coumarin-3-carboxylate(1a)，PEG (600) dibenzo[5,6]coumarin-3-carboxylate(1b), triethylene-glycol di[7-(N,N'-diethylamino)]-coumarin-3-carboxy-late(2a), were synthesized. The cytotoxic effect of these compounds, along with benzo[5,6]coumarin-3-carboxylic acid(1) and 7-(N,N'-diethylamino)-coumarin-3-carboxylic acid(2), against the SGC-7901 cell lines were determined by Sulforhodamine B(SRB) assay. The preliminary cytotoxicity screening process revealed that the investigated dicoumarin derivatives induced 50% inhibition of the cell viability of SGC-7901 cells at micromolar concentrations. Compound 2a was proved superior to compound 1a according to the IC₅₀ values obtained and the agent with PEG moiety has more contribution to cell-killing ability of the molecules than the remaining agents.

Synthesis and Herbicidal Activity of Novel Phenoxysulfonylureas Derivatives

ZHANG Xin-min, ZHENG Liang-yu, GAO Jun-long, LIU Qing-wen, SUN Guo-dong, ......

2009, 25(5):  648-652. 

Abstract ( )   PDF (201KB) ( )  

References | Related Articles | Metrics

Thirteen novel phenoxysulfonylureas derivatives were synthesized, and their structures were confirmed by MS, NMR and element analysis. The herbicidal activity and structure-activity relationship were also investigated. The results of preliminary active tests indicate that the compounds show moderate herbicidal activity.

Isolation and Identification of New Impurities in Nomegestrol Acetate

2009, 25(5):  653-656. 

Abstract ( )   PDF (353KB) ( )  

References | Related Articles | Metrics

Three new and five known steroidal compounds as impurities in nomegestrol acetate(I) were isolated from the enriched mother liquor via various chromatographic methods. Their structures were elucidated by spectrometric analysis and single-crystal X-ray diffraction analysis. New compounds were characterized as 17α-hydroxyl-3-oxoes- trane-5β,17-dicarbonitrile(1), 4-ethyl-17α-hydroxyl-3-oxoestr-4-en-17-carbonitrile(2), 4-ethylestr-4-en-3,17-dione(3). The ¹³C NMR data of known estrane derivatives(4―7) were also reported first time in this paper. The study may be helpful to identifing and characterizing all the impurities that are present at a level of 0.1% and be useful in the quality control of the production of nomegestrol acetate.

Efficient Synthesis of Dicycloalkenopyridines: One-pot Multicomponent Condensation of Aldehydes with Cyclic Ketones

CAI Xi-mei, WANG Qi-fang and YAN Chao-guo*

2009, 25(5):  657-661. 

Abstract ( )   PDF (274KB) ( )  

References | Related Articles | Metrics

Under microwave irradiation, the one-pot multicomponent condensation reaction of three moles of aromatic aldehydes with two moles of cyclic ketones having free α,α'-methylene positions such as cyclopentanone or cyclohexanone in the presence of ammonium acetate and acetic acid afforded dicycloalkenopyridines with two α-arylidene groups in high yields. Under the similar reaction condition, the reaction of aromatic aldehydes with 1-tetralone having only one α-methylene position alternatively resulted in 10-aryl-2,3:5,6-dibenzoacridines.

Synthesis, Structure, and Ring-opening Metathesis Polymerization of η⁵-Pentamethylcyclopentadienyl-(η⁵-exo-tricyclo[5.2.1.0^2,6]deca-2,5,8-trien-6-yl) Iron

ZHAO Xi, LI Bin, XU Shan-sheng, SONG Hai-bin and WANG Bai-quan*

2009, 25(5):  662-665. 

Abstract ( )   PDF (255KB) ( )  

References | Related Articles | Metrics

η⁵-Pentamethylcyclopentadienyl-(η⁵-exo-tricyclo[5.2.1.0^2,6]deca-2,5,8-trien-6-yl) iron(3) was synthesized and characterized by ¹H NMR, ¹³C NMR, MS, elemental analysis, IR, UV and X-ray diffraction analysis. Compound 3 was polymerized with ring-opening metathesis polymerization(ROMP) initiator (PCy₃)₂Cl₂Ru=CHPh. ¹H NMR and IR spectra revealed the presence of CH=CH units in the polymer and supported the ROMP mechanism. GPC analysis of the polymer showed that the weight-average molecular weights(M_w) was 5967, and the polydispersity index(PDI) was 1.16. The polymer was also investigated by UV and cyclic voltammetry.

Construction and Characterization of Lentiviral shRNA Expression Vector Targeting Rat CD40 Gene in Dendritic Cells

2009, 25(5):  666-672. 

Abstract ( )   PDF (1008KB) ( )  

References | Related Articles | Metrics

To construct a lentiviral shRNA vector targeting rat CD40 gene and detect its effectiveness of gene silencing in dendritic cells(DCs), specific siRNA targets with short hairpin frame were designed and synthesized according to the mRNA sequence of rat CD40 gene. DNA oligo was cloned into lentiviral expression vector, and then PCR and sequencing analyses were conducted to verify the constructs. The verified plasmids were transfected into 293T cells that over-express recombinant CD40 in order to select the most effective siRNA targets. shRNA lentiviruses from the selected constructs were propagated and harvested with a virus packaging system, and the virus titers were determined. Western blot and Real-time PCR were performed to determine CD40 expression level in the virus-   infected dendritic cells. PCR and sequencing analyses reveal that shRNA plasmids of four targets were successfully constructed. The optimal interfering target was selected, and the virus with a titer of 5×10⁷ TU/mL was successfully packaged. CD40 expression in rat DCs was knockdown at both mRNA and protein levels by virus infection. In comparison to that of control groups, CD40 mRNA expression and protein expression were decreased by 60.9% and 61.2%, respectively. We have successfully constructed recombinant lentiviral shRNA expression vector targeting rat CD40 gene that can effectively down-regulate CD40 gene expression at mRNA and protein levels in rat DC.

Liquid Chromatography-Electrospray Ionization Mass Spectrometry Method for Determination of Protopanaxadiol in Rat Plasma

WU Yi, TENG Guo-sheng, LIANG Yong-tao, ZHONG Da-fang* and LIU Bing

2009, 25(5):  673-676. 

Abstract ( )   PDF (205KB) ( )  

References | Related Articles | Metrics

A simple, rapid and sensitive method for the determination of protopanaxadiol in rat plasma with ginsenoside Rh₂ as internal standard was developed and validated. The analyte and internal standard were extracted from plasma with ether-dichloromethane(3:2, volume ratio) and then were analyzed by reversed-phase HPLC on a short Zorbax Extend C₁₈ column(50 mm×2.1 mm, 3.5 μm i. d.) eluted with a mobile phase consisting of acetonitrile/methanol 0.10 mmol/L ammonium acetate(45:45:10, volume ratio) at 0.4 mL/min. Detection was performed on an Applied Biosystems Sciex API 4000 mass spectrometer set at unit resolution in the multiple reaction monitoring mode. Electrospray ionization was used for ion production. The assay method shows linear over a range of 5―2000 ng/mL and intra- and inter-day precisions over this range were <10.0% with accuracy ranged from 86.3% to 114.1%. The limit of detection was 500 pg/mL in the plasma. The method was successfully applied to a preclinical pharmacokinetic study of protopanaxadiol(17.5 mg/kg) administered as a single oral dose.

Effect of Regulation of HSV-tk Gene Expression and Tumor Killed Activity with a Single Tetracycline-regulatable Plasmid Vector on HeLa Cells

WANG Qian, DU Zhen-wu, MA Qing-shan, ZHANG Yu-cheng, WU Xiao-dong, ......

2009, 25(5):  677-680. 

Abstract ( )   PDF (277KB) ( )  

References | Related Articles | Metrics

To construct a single tetracycline-regulatable plasmid vector based on the double tetracycline-regulatable plasmid vector system for regulating HSV-tk gene expression so as to effectively kill HeLa cells. Two tetracycline operator(TetO2) was cloned into pcDNA3.1 and a cassette was made for a cytomegalovirus-type 2 tetracycline operator(CMV-TetO2) promoter, and the obtained vector was named pcDNA3.1-CMV-TetO2. Herpes simplex virus thymidine kinase(HSV-tk) gene and tetracycline repressor(TR) gene were cloned into pcDNA3.1-CMV-TetO2 and the two genes were linked with internal ribosome entry site(IRES) to gain a vector named pcDNA3.1-CMV-TetO2- HSV-tk-IRES-TR. The HeLa cells were stablly transfected with pcDNA3.1-CMV-TetO2-HSV-tk-IRES-TR plasmid. The expression of HSV-tk and TR were detected by RT-PCR, the tumorcidal activity of HSV-tk/GCV was determined by MTT assay. In Hela cells transfected with the above plasmid vector, HSV-tk gene and TR gene can be expressed lowly and the concentration of GCV producing a 50% decrease in cell viability was about 50 ?g/mL without adding deoxycycline; in contrast, the expessions of HSV-tk gene and TR gene increased significantly and the concentration of GCV producing a 50% decrease in cell viability was about 5 ?g/mL with adding deoxycycline. Therefore      tetracycline can regulate the expression and tumorcidal activity of HSV-tk gene in HeLa cells with this single plasmid vector.

Extraction and Anti-diabetic Activity on Alloxan-induced Diabetic Mice of Polysaccharides from Huidouba

2009, 25(5):  681-685. 

Abstract ( )   PDF (203KB) ( )  

References | Related Articles | Metrics

The polysaccharide extracted from Huidouba(PEH) exihibited a significant anti-diabetic activity. The polysaccharide contained glucose, mannose and galactose in a content ratio of 1.00:0.34:0.32. After administration with 50― 200 mg/kg body weight of PEH to type II diabetic mice induced by alloxan for four weeks, the blood glucose level of mice was decreased significantly. Moreover, the SOD activity increased at the same time(p<0.01). PEH showed a significant anti-diabetic and anti-oxidation activity. In addition, PEH affected the BUN and ALT levels(p<0.05), which are important characteristics of diabetes mellitus. Through this work, PEH should be a potential anti-diabetic drug in the future.

Regulation of Content of Malondialdehyde by Siqi Decoction via Increasing Activity of Superoxide Dismutase in Blood Serum of Rats with Myocardial Ischemia

SU Yan-bin, JIANG Yi-zhong, LU Ming, CHENG Ying-kun, SU Yan-wen, ......

2009, 25(5):  686-689. 

Abstract ( )   PDF (119KB) ( )  

References | Related Articles | Metrics

Effect of Siqi decoction on myocardial ischemia is to prevent cardiac myocyte membrane from damage associated with oxygen free radicals related to NO. To research the regulatoin of the content of malondialdehyde by Siqi decoction, an index of lipid peroxidation, via increasing activity of superoxide dismutase in blood serum of rats with Myocardial Ischemia, the model of myocardium ischemia was made in Wistar rats with posterior pituitary injection through vein in tail. Siqi decoction, Diaoxinxuekang(DK) and Fufangdanshenpian(FD), the latter two drugs of which are effective TCM drugs of anti-myocardial ischemia at present, were administrated to the rats with myocardium ischemia for 5 days to compare the effect of them on myocardium ischemia as reference drugs via measuring the changes of the content of malondialdehyde and the activity of superoxide dismutase in the rat blood serum with myocardial ischemia. There were a remarkable increase in the activity of superoxide dismutase and a decrease in the content of malondialdehyde in the serum of the rats administered Siqi decoction compared with those of the rats in control group, p<0.05. The contents of MDA in the serum of the prevention group rats in the experiments are lower than those of the cure group rats. Anti-Myocardium Ischemia mechanism of Siqi decoction is the regulation of the content of malondialdehyde via increasing activity of superoxide dismutase in the serum of Rats with myocardial ischemia and stimulating the activity of NOS in serum so as to increase NO concentration.

Refolding and Purification of Yeast Acetyl-CoA Carboxylases CT Domain Expressed as Inclusion Bodies in Escherichia coli

YANG Xue-ying, TAO Jin, ZHENG Liang-yu*, WANG Rui-jian, ZHAO Ke and CAO Shu-gui*

2009, 25(5):  690-694. 

Abstract ( )   PDF (245KB) ( )  

References | Related Articles | Metrics

Acetyl-CoA carboxylase(ACCase) is a crucial enzyme in fatty acid synthesis, by regulating the first committed step in the process. Therefore, it is a potential target for the development of new compounds against   obesity or as herbicides. The cDNA encoding yeast ACCase CT domains(YCTs) from Saccharomyces cerevisiae was amplified by RT-PCR and inserted into the vector PET28a(+) for bacterial expression of YCT fused to N-terminal His-tag(YCT-his6). YCTs-his6 was expressed in Escherichia coli BL21(DE3) PLys as inclusion bodies, which was solubilized in 8 mol/L urea. Ni-agarose chromatography was used to purify the inclusion bodies under denaturing condition. Correct refolding was achieved via systematic dialysis to remove the denaturant gently in the presence of 0.5 mmol/L Triton X-100. The low concentration Triton X-100 was included in the refolding buffer to increase the solubilization and enhance dimeric formation of refolding proteins. The activity of the refolded YCT-his6 was 1.2 U/mg as measured in a spectrophotometric assay using malonyl-CoA as the substrate. To our knowledge, it is the first time that the bioactive YCT-his6 has been expressed successfully in E. coli and isolated from their inclusion bodies.

Expression of Hepatitis B Surface Antigen Genein Ginseng Cells

YU Hai-peng, XUE Yan, AN Wei, LIU Dan, HAO Shu-mei and SHENG Jun*

2009, 25(5):  695-398. 

Abstract ( )   PDF (477KB) ( )  

References | Related Articles | Metrics

The recombinant plasmid pBIBSa containing the HBsAg DNA fragment was transferred into Agrobacterium tumefaciens strain LBA4404 directly. Ginseng cells were transfected with A. tumefaciens carrying pBIBSa and the ginseng cell lines carrying HBsAg-S gene were obtained. The presence of target gene in the transfect cells was confirmed by PCR and RT-PCR. A clear band at the site of 700 bp was observed by agarose electrophoresis analysis of the samples containing the target gene. HBsAg expressed by the transgenic ginseng cells was detected by Western blot. Maximum expression levels of 184 ng HBsAg/g FW and 0. 009% of the total soluble proteins were observed by ELISA. HBsAg in ginseng cells was located both on the cell membrane and in the nuclei.

Effect of Sodium Ferulate on Myocardial Ischemia Fibrosis Induced by Isoproterenol

GAO Hai-cheng, SUN Bo, YU Xiao-yan, GAO Hai-mei, SHI Yan, MIAO Chun-sheng, .....

2009, 25(5):  699-704. 

Abstract ( )   PDF (409KB) ( )  

References | Related Articles | Metrics

We examined whether the powerful sodium ferulate(SF) could improve myocardial ischemia fibrosis degree and gain the information of myocardial energy metabolism via experimental model of myocardial ischemia fibrosis. The model of myocardial ischemia fibrosis was made for the wistar rats induced with 15 mg/kg isoproterenol(Iso) subcutaneous injection. In experiment 1, Iso effective model drug of myocardial ischemia fibrosis at present was administrated to the rats with myocardial ischemia fibrosis and 2, 4, 6, 12, 24, 48 and 72 h, 7 and 21 d later, the changes of adenosine content in rat myocardial tissue and hydroxyproline in blood serum were compared. In experiment 2, SF was administrated to the rats with myocardial ischemia fibrosis and 21 d later, the effect of SF on benazepril as reference drug curing myocardial ischemia fibrosis was evaluated by measuring the changes of adenosine in rat myocardial tissue and hydroxyproline content in blood serum. In the model group, there was a remarkable increase in hydroxyproline content and a decrease in adenosine content of myocardial tissue in experiment 1; there was a remarkable decrease in hydroxyproline in blood serum and a increase in adenosine content in myocardial tissue, which were recovered gradually to control in experiment 2(P<0.05). The results of experiment 1 show that with the increa- sing of pathological change degree, the rat adenosine content reduced gradually and arrived at the lowest value three weeks later(P<0.05); the hydroxyproline content was obviously higher compared with that of control group(P<0.05). The results of experiment 2 show that rat adenosine content in myocardial tissue and hydroxyproline content in blood serum were recovered gradually to normal level after injection SF. The effect of SF against myocardial ischemia fibrosis in preventive group is better than that of improving the myocardial ischemia fibrosis drug. Meanwhile, hinting HPLC is a good method to measure the adenosine content.

Adsorption Site and State of Nitrogen Atom on Ru(0001), (1010) Low-index and (1120), (1121) Stepped Surfaces

DIAO Zhao-yu, YU Hai-yan, WANG Zhong-ni, ZHANG Xue-na and WANG Ze-xin*

2009, 25(5):  705-710. 

Abstract ( )   PDF (406KB) ( )  

References | Related Articles | Metrics

The adsorptions of nitrogen atoms on Ru(0001), (1010) low index surfaces and (1120), (1121) stepped surfaces were investigated by the five-parameter Morse potential(5-MP) method in details. Calculated results demonstrate that N atoms show a tendency to be adsorbed at threefold sites. No subsurface state was found for N atoms on Ru(101??0) surface. There exist 6 stable adsorption sites for N atoms on Ru(112??1) stepped surface which can be classified into 3 types: the on-surface adsorption state, the facet adsorption state and the subsurface state. Moreover, two new perpendicular vibrations at 97 and 98 meV are predicted. All calculated results are in good accord with HR-EELS experiments.

Theoretical Investigation on the Luminescent Properties of Polyfluorene and Poly(fluorene-co-thiophene)

FENG Ji-kang*, ZHANG Jing-hua, REN Ai-min, RAN Xue-qin and LI Yuan-yuan

2009, 25(5):  711-718. 

Abstract ( )   PDF (420KB) ( )  

References | Related Articles | Metrics

The density functional theory was employed to study the structures, ionization potentials(IPs), electron affinities(EAs), and HOMO-LUMO gaps(Δ_H-L) of the oligomers. The time-dependent density functional theory(TD-DFT) and ZINDO were employed to study the lowest excitation energies(E_gs) and the absorption and emission spectra of the oligomers of polyfluorene(PF) and poly(fluorene-co-thiophene)(PFT). By extrapolating Δ_H-L and E_gs to those of infinite chain length, band gaps and effective conjugation lengths of the corresponding polymers were obtained. The IPs, EAs and λ_abs of the polymers were obtained by extrapolating those of the oligomers to the inverse chain length equal to zero(1/n=0). The outcome shows the decreased dihedral angle between fluorene and thiophene units in the PFT compared to that between fluorene units in the PF results in the increased efficient conjugation of PFT. These cause both the maximal absorption and emission wavelengths of PFT red-shifted compared with those of PF.

Preparation, Characterization and Thermal Decomposition Kinetics of the Complexes [Dy(p-NBA)₃Phen]₂·3H₂O and [Dy(m-NBA)₃Phen]₂·4H₂O

XU Su-ling, ZHU Zhi-jia, Ren Ning, LIU Hong-mei, ZHANG Jian-jun*, ......

2009, 25(5):  719-725. 

Abstract ( )   PDF (230KB) ( )  

References | Related Articles | Metrics

The title complexes [Dy(p-NBA)₃Phen]₂·3H₂O(I) and [Dy(m-NBA)₃Phen]₂·4H₂O(II) were synthesized, in the two molecular formulas of which NBA is nitrobenzoate and Phen is 1,10-phenanthroline. The characterizations of the complexes were carried out by means of elemental analysis, UV, IR, XRD and molar conductivity. The thermal decomposition of the two complexes were studied under the non-isothermal condition by DSC, TG-DTG and IR methods in detail. The kinetic parameters of the dehydration process were also obtained by the analysis of DSC curves of the two complexes with Popescu and Vyazovkin methods, respectively,

Electro-optic Properties of DR1 Doped SiO₂ Organic/inorganic Guest-host Films

LIU Shao-lin, YANG Han*, JIN Ru-long, YAN Zhao-xu and YI Mao-bin

2009, 25(5):  726-732. 

Abstract ( )   PDF (348KB) ( )  

References | Related Articles | Metrics

We made a comprehensive investigation on the electro-optic(EO) properties of hybrid sol-gel silica   film doped with Dispersed Red 1 dye(DR1/SiO₂). An important finding is that the dipoles which don’t orient along the direction of corona poling field in the films can be instantaneously poled by alternate modulation electrical field. This instant poling effect results in the EO coefficients dependent on the frequency and intensity of alternate modulation electric field, and some experiments have proved it. We also investigated the electro-optic coefficients and thickness of films at different stir temperatures(T_s) of start solution and at different number densities of DR1.    Experimentally the DR1 number density was optimized to an order of 10²¹/cm³ and a large EO coefficient of γ₃₃=37 pm/V for DR1/SiO₂ film was measured by simple reflection technique at 1 kHz frequencies of modulation electric field. These findings may benefit the practical application of DR1/SiO₂ films in the field of EO modulator and EO probing.

In-situ Investigation of BBr₃/benzene Solution by Fourier Transformation Infrared Spectroscopy

YU Li-li, GAI Li-gang, CUI De-liang* and WANG Qi-long

2009, 25(5):  733-737. 

Abstract ( )   PDF (446KB) ( )  

References | Related Articles | Metrics

By means of the in-situ Fourier transformation infrared spectroscopy(FTIR), the properties of BBr₃/benzene solution, which is usually used as the reactant and solution to synthesize BN by benzene-thermal method, have been investigated. The results show that there are some side reactions between BBr₃ and benzene: (1) BBr₃ as an electron-deficient molecule reacts with benzene at room temperature; (2) below 100 °C, substitution of Br atom for H atom of benzene(ring―H) dominates in BBr₃/benzene solution; (3) cracking of benzene ring occurs at a temperature above 100 °C; (4) decomposition of benzene molecules and formation of long-chain aliphatic compounds feature the spectra of BBr₃/benzene solution collected at above 160 °C. They are unfavor for BN to form when BBr₃ is excessive in the synthesis of BN by benzene-thermal route. On the basis of the experimental results, a coordination reaction mechanism via a η²-C₆H₆ binding mode in BBr3/benzene solution is suggested.

Phosphite Ligand Modified Supported Rhodium Catalyst for Hydroformylation of Internal Olefins to Linear Aldehydes

LI Xian-ming, DING Yun-jie*, JIAO Gui-ping, LI Jing-wei, YAN Li and ZHU He-jun

2009, 25(5):  738-739. 

Abstract ( )   PDF (104KB) ( )  

References | Related Articles | Metrics

A phosphite ligand modified heterogeneous catalyst was developed for the hydroformylation of internal olefins to linear aldehydes, which showed a high activity and high regioselectivity and could be separated easily by filtration after reaction in an autoclave. Three nanoporous silica sieves were used to investigate the influence of pore structure and shape selective performance of support on the regioselectivity to the linear products.

Solid-liquid Metastable Equilibria in Quaternary System Li₂SO₄+Li₂CO₃+Li₂B₄O₇+H₂O at 288 K

SANG Shi-hua*, ZHANG Zhen-lei and LI Ming

2009, 25(5):  740-743. 

Abstract ( )   PDF (186KB) ( )  

References | Related Articles | Metrics

Metastable equilibrium solubilities and densities of quaternary system Li₂SO₄+Li₂CO₃+Li₂B₄O₇+H₂O at 288 K were determined by isothermal evaporation method. According to the experimental data, the metastable equilibrium phase diagram was plotted. The metastable phase diagram had one invariant point F, three double saturated liquid curves E1F, E2F and E3F, and three crystallization fields corresponding to Li₂SO₄·H₂O, Li₂CO₃ and  LiBO₂·8H₂O. It was found that lithium sulphate(Li₂SO₄) had the highest concentration and strong salting-out effects on the other salts. There were no solid solutions or double salts formed in the quaternary system at 288 K.

A Facile Procedure for Conjugate Addition of Amines to Electron Deficient Alkenes with Metal Oxide as Catalyst

LIANG Xue-zheng, GAO Shan and YANG Jian-guo*

2009, 25(5):  744-747. 

Abstract ( )   PDF (201KB) ( )  

References | Related Articles | Metrics

A novel efficient procedure has been developed for the conjugate addition of amines to electron deficient alkenes. A series of metal oxides was synthesized for catalyzing the conjugate addition of amines and alkenes. After optimizing the reaction conditions, SrO was chosen as the most efficient catalyst for the reactions. The results show that the catalyst is very efficient for the conjugate addition of amines to electron deficient alkenes with the excellent yields in several minutes. Operational simplicity, without need of any solvent, low cost of the catalyst used, high yields, reusability, excellent chemoselectivity and applicability to large-scale reactions are the key features of this methodology.

Blends of Poly(lactic acid) with Thermoplastic Acetylated Starch

ZHANG Kun-yu, RAN Xiang-hai, ZHUANG Yu-gang, YAO Bin and DONG Li-song*

2009, 25(5):  748-753. 

Abstract ( )   PDF (330KB) ( )  

References | Related Articles | Metrics

Blends of poly(lactic acid)(PLA) and thermoplastic acetylated starch(ATPS) were prepared by means of the melt mixing method. The results show that PLA and ATPS were partially miscible, which was confirmed with the measurement of T_g by dynamic mechanical analysis(DMA) and differrential scanning calorimetry(DSC). The mechanical and thermal properties of the blends were improved. With increasing the ATPS content, the elongation at break and impact strength were increased. The elongation at break increased from 5% of neat PLA to 25% of the blend PLA/ATPS40. It was found that the cold crystallization behavior of PLA changed evidently by addition of ATPS. The cold crystallization temperature(T_cc) of each of PLA/ATPS blends was found to shift to a lower temperature and the width of exothermic peak became narrow compared with that of neat PLA. The thermogravimetry analysis(TGA) results showed that the peak of derivative weight for ATPS moved to higher temperature with increasing PLA content in PLA/ATPS blends. It can be concluded that PLA could increase the thermal stability of ATPS. The rheological measurement reveals the melt elasticity and viscosity of the blends decreased with the increased concentration of ATPS, which was favorable to the processing properties of PLA.

Synthesis, GC-EIMS, ¹H NMR, ¹³C NMR, Mechanistic and Thermal Studies of o-Xylylene-α,α’-bis(triphenylphosphinebromide)

Muddasir Hanif, LU Ping, XU Hai, TIAN Zhi-cheng, YANG Bing, WANG Zhi-ming, .....

2009, 25(5):  754-759. 

Abstract ( )   PDF (356KB) ( )  

References | Related Articles | Metrics

Organophosphorous compounds containing phosphorus as an integral part have been widely used in industry, organic synthesis and optoelectronics. o-Xylylene-α,α’-bis(triphenylphosphinebromide)(OXBTPPB) is a facile reagent to convert o-quinones(e.g., 9,10-phenanthrenequinone) into polycyclic aromatic hydrocarbons(PAHs). Herein lies an improved synthetic route to OXBTPPB. The resultant was carefully characterized with GC-EIMS, ¹H NMR, ¹³C NMR, spectroscopic techniques. The EIMS shows characteristic peaks at m/z=262.4, 183.3, 108.2, 77.1 attributed to the [C₁₈H₁₅P]^+·, [C₁₂H₈P]⁺, [C₆H₅P]⁺,  [C₆H₅]⁺ ions, respectively. The ¹H and ¹³C NMR spectrum shows well resolved peaks and all the hydrogens and carbons were well-assigned via a combined study of ¹H-¹H COSY, HMBC, and HMQC experiments. The mechanism for the formation of OXBTPPB was proposed based on literature and obtained experimental data. Meanwhile, the thermal stability of OXBTPPB was evaluated with TGA analysis, and an onset decomposition temperature(T_d) was recorded at 323.6 °C.

Effect of C-Tetramethyl Calix[4]resorcinarene Acrylate on Curing Behavior and Film Properties of Thiol-acrylate Coating System

FU Qi and SHI Wen-fang*

2009, 25(5):  760-766. 

Abstract ( )   PDF (418KB) ( )  

References | Related Articles | Metrics

An octa-functional acrylate of C-tetramethyl calix[4]resorcinarene(CMC-4-RA) was facilely synthesized and characterized with ¹H NMR, ¹³C NMR and FTIR spectroscopy. The CMC-4-RA was added to a thiol-acrylate system with different mass ratios, and exposed to a middle pressure mercury lamp. The maximum photopolymerization rate and final vinyl group conversion in the cured film increased greatly along with CMC-4-RA addition that was monitored with Photo-DSC. The tensile strength and pendulum hardness were improved significantly after the addition of CMC-4-RA. With increasing the content of CMC-4-RA to 60%(mass fraction), the glass transition  temperature increased from 34.2 °C to 84.1 °C; the cross-link density was calculated to be increased from 23.83 mmol/cm³ to 82.40 mmol/cm³ according to dynamic mechanical thermal analysis; the thermostability was greatly improved.

Synthesis of Poly(p-phenyleneethynylene)s with Crosslinkable End or Side Groups and Its Solid State Structure and Optical Properties Before and after Crosslinking

WANG Wen-zhong, LIU Zhong-yi and HUANG Peng-cheng*

2009, 25(5):  767-772. 

Abstract ( )   PDF (271KB) ( )  

References | Related Articles | Metrics

Two crosslinkable poly(p-phenyleneethynylene)s(PPEs): poly[2,5-di(2'-ethyl-hexyloxy)-1,4-phenylenee- thynylene] with end-capped vinyl(PPE1) and poly[2,5-di(allyloxy)-1,4-phenyleneethynylene-2,5-di(2'-ethyl-hex- yloxy)-1,4-phenyleneethynylene](PPE2) were synthesized. Via the thermal addition reactions of vinyl end groups of PPE1 and allyloxy side groups of PPE2, crosslinked polymers C-PPE1 and C-PPE2 were obtained, respectively. The two polymers were characterized by wide-angle X-ray diffraction(WXRD), ultraviolet-visible(UV-Vis) absorption, and photoluminescence(PL). The results indicate that in the solid state, the polymer chains of PPE1 were packed with a low degree of crystallinity because of the sterically hindered(2'-ethyl-hexyl)oxy branched side chains, but, because of the introduction of allyloxy side chains, the polymer chains of PPE2 were packed in an order fashion with a high degree of crystallinity. Because of the high crosslinking density in C-PPE2, the formation of aggregates and excimer was hampered by the formed crosslinking network more effectively in C-PPE2 film than in C-PPE1 film.

Research Notes

Synthesis of Ordered Cubic Periodic Mesoporous Silica with High Hydrothermal Stability

LAI Xiao-yong, TU Jin-chun, WANG Hong, DU Jiang, YANG Mei, MAO Dan, ......

2009, 25(5):  773-774. 

Abstract ( )   PDF (197KB) ( )  

References | Related Articles | Metrics

Periodic ordered mesoporous silica materials with Ia3d cubic structure have been successfully synthesized by using ordered cubic mesoporous carbon CMK-8 as template via a nanocasting route, and subsequently characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen sorption measurement. The results reveal that the sample S4 possesses high hydrothermal stability.

Synthesis and Non-linear Optical(NLO) Properties of a Series of Alkoxysilane Derivative Chromophores

SHI Zuo-sen, ZHANG Xiao-long, WANG Shi-wei, ZHAO Li-sha and CUI Zhan-chen*

2009, 25(5):  775-780. 

Abstract ( )   PDF (249KB) ( )  

References | Related Articles | Metrics

A series of chromophores based on benzene and thiophene moieties as π-conjugating spacers were synthesized and then reacted with 3-isocyanatopropyltriethoxysilane (ICTEOS) to give alkoxysilane functionalized chromophores for a sol-gel process. Their structures were confirmed by ¹H NMR, FTIR, HPLC-Ms, UV-visible spectra, element analysis. The thermal properties were characterized by differential scanning calorimetry(DSC) and thermogravimetric analyzer (TGA), they all exhibit good thermal stabilities. Solvatochromic method was used to measure their nonlinear optical properties. The effect of variation of chromophoric structures on NLO properties was investigated, and it indicated that stronger electron-acceptor and longer conjugated bridges produces a considerable red-shift of the absorption maximum and would greatly enhance the molecular quadratic hyperpolarizability (βμ).