Table of Content

10 January 2010, Volume 31 Issue 1

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Contents

Content of Chemical Journal of Chinese Universities Vol.31 No.1(2010)

2010, 31(1):  0. 

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Articles

Growth of Hydroxyapatite on Sulfonated Polybenzimidazole Membranes

HUANG Xia-Yun, SHI Zi-Xing*, YIN Jie

2010, 31(1):  1-6. 

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Organic polymer coated with hydroxyapatite(HA) is an attractive material for the development of tissue repairing application. The abilities of hydroxyapatite incubation on poly [2,2′-(p-oxydiphenylene)-5,5′-bibenzimidazole](OPBI) and sulfonated poly[2,2′-(p-oxydiphenylene)-5,5′-bibenzimidazole](SOPBI) membranes were investigated with the combination of alternate soaking process and simulated body fluid(SBF) soaking methods. Hydroxyapatite phase was analyzed by SAED and ATR-FTIR method. Morphology changes of the hydroxyapatite were observed by SEM. The results show that the use of the SOPBI membranes leads to a higher hydroxyapatite formation rate than that of the OPBI membranes. The sulfonic groups of SOPBI membranes not only offer a negative charged surface to attract Ca²⁺ but also help imidazole groups to bind Ca²⁺. In comparison, OPBI membranes without sulfonic groups decrease formation ability of hydroxyapatite because protonation types of imidazole groups in alternate soaking solutions inhibit interaction between imidazole and Ca²⁺ and HPO₄^2-, which can not be improved by the subsequent SBF soaking.

Facile Microwave Heating Approach to Spiral Cd(OH)₂ Nanowires with 1D Nanostructure

PENG Yin*, LIU Zheng-Yin, LIU Shu-Hua

2010, 31(1):  7-10. 

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We demonstrate a new strategy for the growth of spiral Cd(OH)₂ with 1D nanostructure, yielding an average length of 1—3 μm and width up to 30—100 nm, in one-step process via microwave heating approach. The individual spiral nanowire is made of several smaller nanorods that are aggregated into a bundle. The size of diameter and length of the spiral nanowires are readily tunable by modifying the concentrations of the reactants. Different cadmium salts have more influence on the structure and morphology of the obtained products. The formation mechanism of the spiral Cd(OH)₂ nanowires was discussed. This method may offer an elegant route for the direct growth of metal hydroxide nanowires with potential implications for attachment to electrodes for novel functional devices.

α-Chymotrypsin Immobilization on the Surface of Phase-transferred Fe₃O₄ Nanoparticles

WU Xia, HAN Yu-Shun, CAO Min-Hua, HU Chang-Wen, REN Ling*, GE Guang-Lu*

2010, 31(1):  11-15. 

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The oil-soluble magnetic Fe₃O₄ nanoparticles with uniform size and morphology were synthesized via thermal decomposition of Fe(acac)₃ precursor. They were successfully transferred into aqueous phase through the ligand-exchange reaction with water-soluble PEG diacid molecule, forming water-soluble, stable, nontoxic, and magnetic composite with surface functional group. TEM, M-H curve, FTIR and TGA were used to characterize the as-synthesized composite and demonstrated that the nanoparticles maintained their superparamagnetism and biocompatibility. α-Chymotrypsin(α-ChT) was immobilized on the surface of the water-soluble nanoparticles. The immobilized α-ChT exhibited better thermal stability and high activity after repeated usage.

Electrospinning Preparation and Magnetic Properties of Mn₂O₃ Nanofibers

LI Yue-Jun, CAO Tie-Ping, SUN Xin-Li, SHAO Chang-Lu*

2010, 31(1):  16-19. 

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PAN/Mn(CH₃COO)₂ composite fibers were synthesized via sol-gel process combined with electrospinning technology, using polyacrylonitrile and manganese acetate as precursors. After high temperature calcination, Mn₂O₃ nanofibers were successfully prepared. The samples were characterized by scanning electron microscopy(SEM), fourier transform infrared(FTIR) spectroscopy, thermogravimetry-differential thermal(TG-DTA) and X-ray diffraction(XRD) analyses, respectively. The results show that Mn₂O₃ nanofibers have one-dimensional structure with uniformly distributed diameter. Magnetic property measurements suggested that the Mn₂O₃ nanofibers exhibited ferromagnetic-anti-ferromagnetic-paramagnetic property.

Fabrication and Characterization of Y₂O₃∶Yb³⁺,Er³⁺ Upconversion Nanofibers by Electrospinning

DONG Xiang-Ting*, LIU Li, WANG Jin-Xian, LIU Gui-Xia

2010, 31(1):  20-25. 

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PVA/[Y(NO₃)₃+Yb(NO₃)₃+Er(NO₃)₃] composite nanofibers were fabricated by electrospinning. Y₂O₃∶Yb³⁺,Er³⁺ upconversion nanofibers were obtained by calcination of the relevant composite nanofibers. XRD analysis reveals that composite nanofibers are amorphous in structure, and Y₂O₃∶Yb³⁺,Er³⁺ upconversion nanofibers are cubic in structure with space group Ia3. SEM images indicate that the mean diameter of the composite nanofibers is ca. 150 nm, and the diameter of the fibers gradually decrease with the increase of calcinations temperature. Y₂O₃∶Yb³⁺,Er³⁺ upconversion nanofibers of 60 nm in average diameter were acquired at 600 ℃. TG-DTA analysis reveals that the water, organic compounds, nitrates in the composite nanofibers are decomposed and volatilized totally, and the mass of the sample kept constant when sintering temperature is above 600 ℃, and the total mass loss percentage is 83%. FTIR analysis manifest that the spectrum of the composite nanofibers is basically the same as that of the pure PVA, and Y₂O₃∶Yb³⁺,Er³⁺ upconversion nanofibers are formed above 600 ℃. The upconversion spectroscopic properties of the Y₂O₃∶Yb³⁺,Er³⁺ nanofibres were investigated under the excitation of a 980 nm continuous wave diode laser. Y₂O₃∶Yb³⁺, Er³⁺ nanofibres emitted strong green and red upconversion emissions centering at 521, 562 and 656 nm, respectively. The green emissions were attributed to the transitions of ²H_11/2/⁴S_3/2→⁴I_l5/2 energy levels of Er³⁺ ions, and the red emission was assigned to the transition of ⁴F_9/2→⁴I_l5/2 energy levels of Er³⁺ ions. The formation mechanism of Y₂O₃∶Yb³⁺,Er³⁺ upconversion nanofibers was advanced. The technique can be applied to fabrication of other rare earths composite oxides upconversion nanofibers.

Synthesis and Photoluminescence of a Novel Full-color Emitting Phosphor NaCaPO4∶Dy3+

LUO Zhi-Tao, WANG Yu-Hua*, LI Ye-Zhou

2010, 31(1):  26-29. 

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A series of single-phase full color phosphors, NaCaPO₄∶Dy³⁺ was prepared using conventio-nal solid state reaction. The luminescent properties were studied under ultraviolet(UV) and vacuum ultraviolet(VUV) excitation. The UV excitation spectra reveal that the samples have a series of peaks at around 250—500 nm, with the highest peak at around 350 nm. The samples can absorb the emission of ultraviolet photons and emit visible light efficaciously. The VUV excitation spectra of the samples reveal that there are absorption bands at VUV region. The samples can absorb the vacuum ultraviolet photons and translate to visible light efficaciously. All the chromaticity coordinates of the samples are in the white region under both UV and VUV excitation. It can be predicted that this novel material can be applied both in LEDs and in mercury-free fluorescent lamp.

Letters

Synthesis and DNA Adsorption Properties of Hierarchically Macro-mesoporous Titania Films

ZOU Yong-Cun, LU Feng-Guo, LI Guo-Dong*

2010, 31(1):  30-32. 

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Titania thin films with hierarchically macro-mesoporous were prepared by the addition of bulky organic molecule(1,3,5-trimethylbezenze) in aqueous solution of F127(EO₁₀₆PO₇₀EO₁₀₆). After calcined at 673 K, ordered thin films with cubic meso-structure and macropores were formed. DNA(Cytochrome c) was used as probe to study the adsorption ability of macromolecules on this film. The hierarchically macro-mesoporous films show high adsorption ability of DNA molecules compared with conventional titania films and mesoporous titania films, which is attributed to the presence of macropores.

Articles

Electrochemical Behavior and Determination of Indole-3-acetic Acid at NanoAu/MWNTs/chitosant Sensor

ZHANG Xue-Yu, LIU Xing-Mei, LIU Wei-Lu, YANG Ming*, ZHANG Zhi-Quan*

2010, 31(1):  33-37. 

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This study was making use of chitosant as a dispersion medium of multi-walled carbon nanotubes(MWNTs) and formed a stabilizating nanoAu-MWNTs-CS-GCE layer via MWNTs/chitosant with positive charges adsorption of nanoAu with negative charges. Electrochemical method was selected to investigate the performance of the modified electrode and the electrochemical behavior of indole-3-acetic acid. The catalytic current of IAA versus its concentration had a good linearity in a concentration range of 5—200 μmol/L at around -0.78 V with a detection limit of 8.33×10^-6 mol/L and a correlation coefficient of 0.9997.

Experimental Optimization of Sample Pretreatment for Fingerprinting of Chemical Components in Tea

ZHAO Rui, OUYANG Jie, DU Shu-Shan, GENG Zhu-Feng, XU Mei-Feng, DENG Zhi-Wei

2010, 31(1):  38-45. 

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A certain pattern recognition method was suggested to optimize the experimental conditions of the sample pretreatment for chemical finger-print experiments. ¹H NMR plus Principle component analysis(PCA) were used as the testing and evaluating means, considering that the test samples of finger-print experiments usually consist of multi-components. The data exposed in ¹H NMR spectra were wholly involved in PCA to provide the predictable information for the design of the sample pretreatment. With this sleight, we optimized the experimental conditions such as the prescription of extraction solution, ratio between solution and sample, experimental temperature and extraction duration, and proposed a standard procedure of the sample pretreatment for ¹H NMR finger-print experiments of tea. Finally, the newly designed procedure was tested with four tea samples and the ¹H NMR spectra obtained were well matched the requirements of chemical finger-print experiments. The results show that this method is reliable and can be used in designing a standard procedure of sample pretreatments for complicated testing system.

Serum EFAs and NEFAs Metabolic Profiling Analysis Child-bearing Age Women and Its Application to NTDs Preventive Nutrition Intervention

HAN Li-Da, LIANG Qiong-Lin, WANG Yi-Ming, LUO Guo-An*

2010, 31(1):  46-50. 

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Nutrition intervention(NI) is the common means for Neural tube defects(NTDs) prevention. The serum EFAs and NEFAs metabolic profiling of Child-bearing age women was studied by GC/MS method. The subjects were random divided into two groups: NI group(n=48) and control group(n=48). The mean levels of EFAs and NEFAs were reported. PLS-DA using the SIMCA-P software package allowed the different group to be distinguished, which means NI has great effects on the metabolism of fatty acids. Based on the quantification results, six FAs(both EFAs and NEFAs) were recognized as potential biomarkers. And the relationship between NI and the FAs′ concentration variation was discussed to illustrate the potential impacts on the incidence of NTD.

Post-chemluminescence Reaction of Some Nitrogenous Organic Compounds in the N-Chlorosuccinimide-dichlorofluorescein System

ZHANG Hui-Zhong, NIE Fei, Lü Jiu-Ru

2010, 31(1):  51-56. 

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The post-chemiluminescence behavior of fifty three kinds of nitrogenous organic compounds was studied in the N-chlorosuccinimide-dichlorofluorescein system. Many substances were found to have the post-chemiluminescence activity in the system. After the analysis for the structure of these nitrogenous organic compounds, it was found that the state of the N atom in the molecules was important to the post-chemiluminescence activity and the post-chemiluminescence intensity of the nitrogenous organic compounds. The possible reaction mechanism of the post-chemiluminescence reaction was proposed based on the studies of the chemiluminescence kinetic characteristics, the chemiluminescence spectra and the fluorescence spectra of some related substances. The application value of these post-chemiluminescence reactions in analytical chemistry was estimated.

Metabonomics Research of the Influence of Melamine to the Urine Metabolism of the Children Based on UPLC/TOF-MS

WANG Yong, JIANG Zhi-Ting, LIANG Qiong-Lin, WANG Yi-Ming, WANG Mei, ...

2010, 31(1):  57-60. 

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The metabonomics method was employed to investigate the possible influence of melamine to the urine metabolism of the children. Urine samples of 7 melamine affected children and 570 healthy children were collected from the Children Hospital of Changchun. The profiles of the collecteed urine samples were obtained with ultra performance liquid chromatography coupled with time-of-flight mass spectrometry(UPLC/TOF-MS). The data were firstly processed with the software MarkerLynx, then analyzed with principle component analysis(PCA) and partial least squares discriminant analysis(PLS-DA). The potential biomarkers were screened out according to the VIP(variable importance in projection) value and identified with i-fit and database. Most of the metabolites of significant intergroup differences were finally found to be in the tricarboxylic acid cycle. According to the biological functions of the obtained potential biomarkers, it was deduced that the citric acid metabolism was disturbed by melamine through its kidney injury effect. The results suggest that the metabonomics method can be utilized to investigation of the influence of melamine to the metabolism as well as the noninvasive examination of the melamine caused kidney injury.

Letters

Observation of Surface Plasmon-coupled Directional Fluorescence Using Thin Iron Films

CAO Shuo-Hui, XIE Tang-Tang, CAI Wei-Peng, LI Yao-Qun*

2010, 31(1):  61-63. 

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The observation of surface plasmon-coupled directional fluorescence(SPCDF) on thin iron films was presented. SPCDF from thin iron films was p-polarized with a directional emission angle of 70°. Fluorescein and meso-tetra(4-sulfonatophenyl)porphine(TPPS) were used as a model system of dual fluorophores. Using 25 nm thin iron films, the SPCDF signals of the two fluorophores were observed at a fixed angle just by one scan. The SPCDF signals of Fluorescein and TPPS added to whole blood were identified clearly, eliminating the background interference of blood effectively. Thin iron films have been proven to be new materials for SPCDF detection, promoting a new mode to observe the enhanced fluorescence signals of different fluorophores by one scan. They should be useful for tracking the labled systems of multi-fluorophores in biological applications.

Articles

Synthesis and Biological Activity of New Trifloromethyl-pyrimidine Phenylsulfonylurea Derivatives

WANG Hong-Xue, LI Fang, XU Li-Ping, LI Yong-Hong, WANG Su-Hua, LI Zheng-Ming*

2010, 31(1):  64-67. 

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Seventeen new sulfonylurea derivatives with trifloromethyl group in the pyrimidine ring were designed and synthesized, based on NK92825 and NK94827. Their structures were confirmed by ¹H NMR and elemental analysis. Preliminary herbicidal activities of these new sulfonylurea compounds were determined by pot bioassay experiments at dosage of 375 g/ha. The results show that some derivatives display good heribicidal activities.

Synthesis and Asymmetric Henry Reaction of Menthyl Arylglyoxylate

XIANG Ji-Ming, LI Bao-Lin*

2010, 31(1):  68-73. 

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In the presence of titanium(Ⅳ) tetraethoxide, eight chiral menthyl arylglyoxylates were prepared by transesterification of ethyl arylglyoxylates and the natural (1R,2S,5R)-(-)-menthol. Seven new menthyl (2R)-2-hydroxy-2-aryl-3-nitropropionates were synthesized by the Henry reaction of menthyl arlglyoxylates and nitromethane. The structures of the products were characterized by IR, ¹H NMR, ¹³C NMR spectroscopy, MS and elemental analysis. The diastereoselectivities were analyzed by HPLC with chiral column. The diastereomeric excess(d.e.) of the condensation reactions were between 46.5%—64.2%, achieve diastereoselectivities control to the structure.

Synthesis, Antioxidation Activity of Bridged Vinyl-8-hydroxyquinolin Derivative and Its Induction Proliferation of Mesenchymal Stem Cells

ZHANG Pei-Quan1*, ZENG He-Ping2

2010, 31(1):  74-78. 

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2-Vinyl-8-hydroxyquinolin derivative(6) was synthesized and characterized by IR, UV-Vis, 1H NMR, MS and elemental analysis. Meanwhile, the title compound was biologically evaluated by the MTT assay on the proliferation of rat mar-row-derived mesenchymal stem cells(rMSCs) and by the DPPH· method on the antioxidation activity. The results show that the title compound can induce the proliferation of mesenchymal stem cell compared with the control group under a low concentration condition and inhibitive effect on a higher concentration condition. The results also show that compound 6 has strong antioxidation activity. With concentration increasing, antioxidation activity is first increased and then decreased. It was found that the increasing antioxidant property of this protein depended quantitatively on the increase of its the compound 6 content.

Design, Synthesis and Crystal Structure of 1′-Iodoferrocenecarbaldehyde Oxime Esters

GUO Jian2, WU Kai-Qiang2, CHEN Xin2, YUAN Yao-Feng1,2*

2010, 31(1):  79-83. 

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The multi-functional 1′-iodoferrocenecarbaldehyde is a versatile building block in organic synthesis. Four novel 1′-iodoferrocenecarbaldehyde oxime esters were designed and synthesized on the basis of 1′-iodoferrocenecarbaldehyde. The compounds were confirmed by means of elemental analysis, IR spectrum, 1H NMR, MS and X-ray single-crystal diffraction analysis. The crystal of compound 3a belongs to a monoclinic system, space group P2(1)/n with cell parameters a=0.6328(3) nm, b=1.0634(7) nm, c=2.3815(13) nm, α=90°, β=93.546(19)°, γ=90°, Z=4, μ=2.883 mm-1, Dc=1.910 g/cm3, F(000)=896. The crystal structure of compound 3a shows that the molecules can form three-dimension supramolecular cavity assemblies via hydrogen bond, static interaction and aromatic π-π stacking interactions. This special assemblies could selectively recognise some of the guest molecules.

Isolation and Identification of a New Compound from the Roots of Picrorhiza Scrophulariiflora

YIN Li-Zi1, OUYANG Ping1, XU Xue1, ZHOU Li-Guang1,2, WANG Da-Cheng1, DENG Xu-Min

2010, 31(1):  84-87. 

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Xizang Huhuanglian, the roots of Picrorhiza scrophulariiflora Pennell, is a traditional Chinese Medicine used to treat damp-heat dysentery, jaundice, indigestion, common fever, acute viral hepatitis, and steaming of bone. The scholars of domestic and foreign have studied on the pharmacological effects of the plant, and found that the plant will be one of the most effective preparation in protecting the liver. This plant is rich in terpenoids, iridoid glycosides, phenolic glycosides and phenylethanoid glycosides. These compounds of the plant were isolated via silica gel column, D101 macroporous column, Sephadex LH-20 column, ODS column chromatography and HPLC. The structures of these compounds were identified by spectroscopic methods(NMR, IR, UV and MS) and chemical methods. Four compounds from this plant were obtained. Their names are Scrophenoside E(1) [(6-(4-acetyl-2-methoxyphenoxy)-3,5-dihydroxy-4-(3,4,5-trihydroxy-6-(hydroxymethyl)tetrahydro-2H-pyran-2-yloxy)tetrahydro-2H-pyran-2-yl)methyl-3-methoxy-4-(3,4,5-trihydroxy-6-(hydroxymethyl)tetrahydro-2H-pyran-2-yloxy)benzoate], Coniferin(2), Arbutin(3) and Androsin(4). Scrophenoside E is a new compound. Coniferin, Arbutin and Androsin are three known compounds.

Activity Assay and Mechanism Study of Bisphosphonates as Matrix Metalloproteinase Inhibitors

LIU Xing-Chen1, LI Hong-Wei1, WANG Ye2, JIANG Kun2, FANG Xue-Xun2, WU Yu-Qing1*

2010, 31(1):  88-93. 

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Matrix metalloproteinases(MMPs), a group of zinc-dependent metalloproteinases, are responsible for the hydrolytic breakdown of extracellular matrix. Aberrantly over expression of MMPs has been associated with much human pathology including cancer, arthritis, and heart disease etc. Therefore, the development of MMPs inhibitors to drugs has always been of great interest to scientific institutions. Bisphosphonates were reported to be a new kind of MMPs inhibitors with great potential. According to the 3-dimensional structure, 4 bisphosphonates are designed, synthesized and tested against several typical MMPs. The inhibitory activities toward MMP-2, MMP-3 and MMP-9 were tested in vitro using flourometric method. The results show micromolar-level activity and modest selectivity toward MMPs. Molecular docking study and fluorometic titration spectra were performed to reveal the recognition and inhibition mechanism between MMPs and bisphosphonates, and the binding mode between them was proposed.

Theoretical Study on the Polarizability and the Second Hyperpolarizability of Benzo-bisdithiazolyl Dimer Radical

DU Yan-Qing1, QIU Yong-Qing1*, SUN Shi-Ling1, SUN Xiao-Na1, SU Zhong-Min1, WANG

2010, 31(1):  94-99. 

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The quantum chemistry UMP2/6-31G(d,p) method was used to optimize the structure of benzo-bisdithiazolyl dimer radical. Furthermore, the DFT UB3LYP/6-31G(d,p) approach was adopted to calculate the polarizability and the second hyperpolarizability of the five pointes of radical in which the interplanar distance was enlarged and shorten by a step of 0.05 nm. According to UMP2 calculations, the radical with singlet state is the stable one. For the vertical-stacking radical, the polarizabilities of the radical with singlet and triplet state increase with increasing the interplanar distance, while only the second hyperpolarizabilities of the radical with triplet state increases with increasing the interplanar distance. For the shifted-stacking radical, the polarizability of the radical with singlet decreases with increasing the interplanar distance, the absolute value of the second hyperpolarizability increases with increasing the interplanar distance for the radical with triplet shifted-stacking radical.

Theoretical Studies for One- and Two-photon Absorption Properties of 3,6- and 2,7-Carbazole Derivatives

LI Wen-Chao1, FENG Ji-Kang1,2*, REN Ai-Min1, SUN Chia-Chung1, YU Xiao-Qiang3, WA

2010, 31(1):  100-105. 

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The density functional theory(DFT)/B3LYP associated with ZINDO/SDCI methods were used to calculate the molecular geometries, electronic structures, one-photon and two-photon absorption properties of 3,6- and 2,7-carbazole derivatives. The position of vinylpyridine substituents affects the properties of one-photon absorption(OPA) and two-photon absorption(TPA). Compared with 3,6-carbazo derivatives, the OPA wavelengths of 2,7-carbazole derivatives are bathochromic shift and the oscillator strength increased; the TPA wavelengths are red-shifted and the TPA cross-section increased. 2,7-carbazole derivatives will be more promising TPA materials.

Theoretical Study on the Diels-Alder Reactions Between Germabenzenes and Dienophiles

WANG Yan1*, ZENG Xiao-Lan1, FANG De-Cai2

2010, 31(1):  106-111. 

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Density functional theory(DFT) calculations, at the B3LYP/6-311G(d,p) level of theory, were performed to study the reaction mechanism and potential energy surface of the Diels-Alder reactions between germabenzenes and some dienophiles. The influences of substituents and benzene as a solvent on the potential energy surface of the hetero-Diels-Alder reactions were investigated and the origin of regioselectivity in the he-tero-Diels-Alder reactions was explored. Our calculation results show that all of studied reactions proceed in a concerted way. The influences of phenyl at C atom of dienophiles on the asynchronicity in the bond-formation process and activation barrier of reaction are closely related to the relative position of phenyl with respect to Ge atom in products. The CCl3 group at Ge atom of germabenzene molecule is in favor of process of the hetero-Diels-Alder reactions and solvent effect is not crucial for the potential energy surfaces of the studied reactions. The present calculations reproduce the regioselectivity observed experimentally in hetero-Diels-Alder reactions, which indicates that the kinetic factor controls the reaction proceeding.

Preparation of Mesoporous TiO2/CdS Thin Film Photoelectrode Through Electrodeposition

ZHOU Wei1,2, FU Hong-Gang1,2*, PAN Kai2, TIAN Chun-Gui2, TIAN Guo-Hui2, REN Zhi-

2010, 31(1):  112-116. 

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Mesoporous TiO2/CdS thin film photoelectrode was successfully prepared by electrodeposition CdS nanoparticles on mesoporous TiO2 thin film. The products were characterized by XRD, SEM, Raman, SPS and UV-Visible spectra. The results revealed that CdS nanoparticles were successfully deposited on the surface and in the hole of mesoporous TiO2 thin film. The photoelectric property of these films were investigated by photocurrent action spectra. The results show that the composite films exhibited enhance photoelectric conversion efficiency compared with mesoporous TiO2 thin films. This may be attributed to the character of CdS and the formation of mesoporous TiO2/CdS heterojunction.

Differential Model of Benzene Absorption in a Hollow Fiber Membrane Contactor by N-Formylmorpholine

XU Jun, LI Rui, WANG Lian-Jun*, LI Jian-Sheng, SUN Xiu-Yun

2010, 31(1):  117-124. 

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A differential equations mathematical model was developed for the transport of benzene through hollow fiber membrane in the presence of an aqueous N-formylmorpholine(NFM) solution. The model was based on “non-wetted mode” and the laminar parabolic velocity profile was used for the gas flow in the tube side, whereas, the liquid flow in the shell side was characterized by Happel′s free surface model. The effects of various factors such as gas and liquid flow rates, gas and liquid feeding concentration, flow pattern, membrane inner radius and membrane number on mass transfer were simulated. Moreover, the simulation results were validated with the experimental data and it was found the simulation result agreed with the experimental data well.

ab initio Study on the Spectroscopy of H2CCC

SHU Xin, ZHAO Zeng-Xia, ZHANG Hong-Xing*, SUN Chia-Chung

2010, 31(1):  125-129. 

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Complete active space self-consistent field(CASSCF) calculations with ANO-S basis sets were performed for a few electronic states of propadienylidene, H2CCC, and its cation and anion in C2v symmetry. For all the calculated states, the accuracy of the total energies was improved by including dynamic electron correlation via the multiconfiguration second-order perturbation theory(CASPT2) method. The results suggest that the calculated transitions of X1A1 → 1A2, X1A1 → 1B1 and X1A1 → 21A1 at 159.0, 216.5 and 476.4 kJ/mol are attributed to π(b2)→π*(b1), n(a1)→π*(b1) and π(b1)→π*(b1) transition, respectively. The electron affinities were obtained in comparison with the photoelectron spectrum(PES) data. These above results are in agreement with the previous experimental data.

Effect of Carburization Temperature on the Preparation and the Catalytic Performance of Molybdenum Carbide in the Dry-methane Reforming(DMR)

CHENG Jin-Min, HUANG Wei*, ZUO Zhi-Jun

2010, 31(1):  130-134. 

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A series of molybdenum carbide catalysts were prepared using 20%CH4-H2 to carburize molybdenum trioxide at different temperatures. The catalysts were characterized using X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS) and N2-adsorption. Their catalytic performance was evaluated in the model reaction of the dry-methane reforming(DMR) to synthesis gas. Here, the characteration of bulk and surface Mo2C catalysts and its influence on the catalytic performance were described. The results show that the more pure crystalline phase of β-Mo2C is obtained when the Mo2C catalyst is prepared at carbonization temperature above 700 ℃. The carburization degree was improved and free carbon on the surface was increased with increase of carbonization temperature. The catalyst prepared at carbonization temperature of 800 ℃ shows the best catalytic performance. The result indicated that high carburization degree and the appropriate amount of free carbon on the surface could promote carbonation and oxidation balance of Mo2C catalyst and favor the catalyst activity and stability.

Adsorption Behavior and Mechanism of Nano-Al2O3 for Ge(Ⅳ)

ZHANG Lei*, LI Hong-Mei, HAN Guang-Xi, KANG Ping-Li

2010, 31(1):  135-140. 

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The effects of various equilibrium time, temperature and pH on the adsorption of Ge(Ⅳ) on nano-Al2O3 were studied. The results show that the adsorption is fast to reach equilibrium within 2 min. It was found that the adsorption efficiency of Ge(Ⅳ) was more than 95% with pH from 4 to 11. Almost all of Ge(Ⅳ) ions adsorpted onto nano-Al2O3 can be eluted with 0.3 mol/L K3PO4-1 mol/L H2SO4 mixed solution within 5 min, the desorption percentage can reach 97%. The sorption of Ge(Ⅳ) ions onto nano-Al2O3 followed the second-order rate equation, the kinetic experimental data properly correlate with the second-order kinetic model and the values of activation energy(Ea) was 11.63 kJ/mol. The adsorption data are fitted to the Freundlich and the magnitude of sorption energy computed from D-R equation is 10.87 kJ/mol, thus, the type of the adsorption of germanium on nano-Al2O3 is a chemical adsorption. The ΔG0 and ΔH0 values is negative and positive respectively which indicate the adsorption of Ge(Ⅳ) on nano-Al2O3 is spontaneous and endothermic.

Visible Photocatalytic Activity of Flowerlike Cu2O/Cu Nanocomposites

ZHOU Bo1, LIU Zhi-Guo1*, WANG Hong-Xia2*, ZHAO Li-Jun1, LIU Wei-Long1, SU Wen-Hu

2010, 31(1):  141-144. 

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Cu2O/Cu nanocomposites with flowerlike nano-architecture were prepared using a template-free two-step hydrothermal synthesis route. The phase-structure, morphology and specific surface area were characterized by the X-ray differction(XRD), scanning electron microscope(SEM), high resolution transmission electron microscope(HRTEM) and automatic adsorption. The photocatalytic property of the composite catalyst was characterized by phtodegradation on Procion Red MX-5B under visible-light illumination. Compared with Cu2O and P25, the flowerlike Cu2O/Cu nanocomposites exhibit higher photocatalytic performance on photodegradation of Procion Red MX-5B under visible-light illumination due to the interaction between Cu2O and Cu, indicating that they are good candidates for the processing of pollutants.

Effects of the Active Carbon Surface Properties on the Structure and Catalytic Activity of Cu2O/AC Catalyst

LI Zhong*, WEN Chun-Mei, ZHENG Hua-Yan, XIE Ke-Chang

2010, 31(1):  145-152. 

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The chloride-free Cu2O/AC catalyst was prepared by pyrolysis of copper acetate supported on active carbon(AC), which was used to catalyze the direct vapor-phase oxycarbonylation of methanol to dimethyl carbonate(DMC).When the AC support was treated with nitric acid or ammonia, the chemical property of AC surface was modified, resulting in the change of surface structure and high catalytic activity of Cu2O/AC catalyst. The experiments revealed that the new nitro-groups were formed and the oxy-groups(C—O—C, C—O and CO—O) increased, but the CO species decreased significantly or disappeared on the surface of active carbon treated with nitric acid or ammonia. The reduction of CuⅡ to CuⅠwas promoted by the nitro-groups electron donation and rich CO—O groups, which was propitious to obtain unique and well dispersed Cu2O supported catalysts and enhance the catalytic activity. The treatment of AC with ammonia was favor for the dispersion of Cu2O and improved catalytic activity furthermore. On the conditions of n(CO)∶n(MeOH)∶n(O2)=4∶10∶1 and SV=5600 h-1, the methanol conversion, the space time yield and the selectivity of DMC reached 7.0%, 145.1 mg/(g\5h) and 68.7%, respectively.

Electrocatalytic Performances of MmNi3.2Al0.2Mn0.6Co1.0 Modified with MnO2 for NaBH4 Oxidation

WANG Gui-Ling1*, CHENG Yuan-Hui1, ZHANG Wei-Cai1, LU Tian-Hong2, CAO Dian-Xue1,

2010, 31(1):  153-156. 

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The effect of KOH treatment and MnO2 adulteration of the MmNi3.2Al0.2 Mn0.6Co1.0(Mm is misch metal) on the electrocatalytic activity for borohydride oxidation was investigated by the linear sweeping voltammograms test. It was found that the peak potential and current density of the NaBH4 oxidation at the MmNi3.2Al0.2Mn0.6Co1.0 catalyst without any treatments are -0.65 V and 14 mA/cm2, respectively. After KOH treatment, the peak potential remains the same, but the peak current density reached 50 mA/cm2, which is 3.6 times of that at the un-treated MmNi3.2Al0.2Mn0.6Co1.0. KOH treatment followed by the MnO2 adulteration further increased the electrocatalytic activity of the MmNi3.2Al0.2Mn0.6Co1.0. When the mass fraction of MnO2 to MmNi3.2Al0.2Mn0.6Co1.0 is 10%, the peak potential and current density are -0.45 V and 126 mA/cm2, respectively. The peak current density is 2.5 and 9 times of that at the MmNi3.2Al0.2Mn0.6Co1.0 with and without KOH treatment, respectively.

Preparation and Investigations on Platinum Catalysts Supported on Self-assembled Films of Gold Nanoclusters

ZHANG Yu-Min, LIU Hai-Yan, SONG Wen-Bo*

2010, 31(1):  157-161. 

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Special attention was focused Pt-based and Pd-based metallic catalysts because of their broad industrial applications such as fuel cells, they had themselves merit. However, the high cost of platinum catalysts, slow reaction kinetics, poor selectivity, and catalyst poisoning have so far precluded the widespread use of fuel cells. Pt-based bimetallic catalysts may enhance catalytic activity, as compared to monometallic catalysts. This work demonstrated the use of self-assembled gold nanoclusters films for loading platinum catalysts. The self-assembled gold nanoclusters films were prepared based on the electrostatic interactions between the terminated cationic groups attached on the gold nanoclusters surfaces and the negatively charged polyelectrolyte binding layer and used to confine the growth of platinum metal catalyst by electrodeposition. The result revealed that the electrodeposited Pt was greatly accelerated by the underlying self-assembled gold nanoclusters films, and the activity towards oxidation of formic acid was dramatically increased compared with those of Pt electrodeposited on the surfaces of bare as well as the electrode covered with polymer binding layers. Present study provides a simply controlled test-bed for fundamental study on using self-assembled gold nanoclusters films as a support for catalysis.

Power Generation in Bio-cathode Microbial Fuel Cell with Different Cathode Materials

ZHANG Jin-Na, ZHAO Qing-Liang*, YOU Shi-Jie, ZHANG Guo-Dong

2010, 31(1):  162-166. 

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Power generation from bio-cathode microbial fuel cell(MFC) with graphite fiber brush(GFB) and graphite granule(GG) as cathode material was investigated with COD(Chemical Oxygen Demand) of 2000 mg/L glucose as anodic fuel. The results demonstrated that GFB-cathode MFC could be started up after a longer time with lower voltage of 0.324 V than GG-cathode MFC(0.581 V) at constant load of 300 Ω. Polarization analysis showed that the maximum power density of 24.7 W/m3(117.2 A/m3) and 50.3 W/m3(167.2 A/m3) were reached for GFB-cathode MFC and GG-cathode MFC, respectively. As indicated by electrochemical impedance spectroscopy(EIS) analysis, the difference in power output of two MFCs should result from internal resistance, particularly activation resistance. This is mainly because of the difference in surface feature of two materials for microbial growth and distribution. Organic compounds could be removed in both MFC systems, which accomplished waste water treatment.

Synthesis and Self-assembly of Thermo-sensitive β-Cyclodextrin Containing Copolymers

REN Shen-Dong, CHEN Dao-Yong, JIANG Ming*

2010, 31(1):  167-171. 

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A novel thermo-sensitive β-cyclodextrin pendent poly(N-isopropylacrylamide)(PnipamCD) was prepared, which had a higher lower critical solution temperature(LCST) than that of pure poly(N-isopropylacrylamide)(PNIPAM). In its aqueous solution, spherical micelles were obtained as temperature increased rapidly while hollow vesicles were obtained as temperature increased slowly. In addition, rod-like aggregates were achieved in acetone, a selective solvent of PNIPAM.

Physical Gelation and Structures of P123 in D2O Solution

TANG Jian-Kai, SUN Zhao-Yan*, AN Li-Jia

2010, 31(1):  172-176. 

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1H NMR was used to study the sol-gel transition of triblock copolymer P123(PEO20PPO70PEO20, 30%) in D2O solution by analyzing the half-height width and the chemical shift of the proton signals of the P123. The changes of gel structures for P123(30%) was investigated with rheological method and synchrotron radiation(SR). With the increase of temperature, the transition of gel phases from fcc+hcps to hcp structure and finally to lamellar structure were found. Moreover, the phase separation occurred for the P123 in D2O solution at high temperature.

Synthesis of a Fullerene End-capped Poly(ε-caprolactone) by Fullerene Derivative Initiator

PENG Qi-Yun, KANG Feng, LI Juan, YANG Xin-Lin*

2010, 31(1):  177-180. 

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Using N-substituted 3,4-fullero pyrrolidine with an active hydroxyl group as an initiator, polymerization of ε-caprolactone was performed via ring-opening polymerization. The product was characterized by 1H NMR, 13C NMR and MALDI-TOF MS and its thermal properties were determined by TG and DSC. The results show that a fullerene end-capped poly(ε-caprolactone) is achieved, and the product is more thermally tolerative than poly(ε-caprolactone).

Effect of Cu2+ upon the Fluorescent Properties of Dendrimer PAMAM-FCD

HAN Qiao-Rong1,2, WANG Bing-Xiang2, DING Ma-Tai1, HE Xu-Min1*

2010, 31(1):  181-185. 

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Dendrimer of polyamidoamine PAMAM was modified with 2-fluorenecarboxaldehyde(FCD)to form dendrimers PAMAM-FCD of generation one, two and three, respectively. Structures and properties of PAMAM-FCD were characterized by IR, 1H NMR and MALDI-TOF-MS, with special attention being paid to the effect of Cu2+ on the fluorescent and UV spectra of these dendrimers. The results show that, even though Cu2+ usually behaves as a fluorescence quencher, it can significantly enhance the fluorescence of these dendrimers. Furthermore, the absorbance of PAMAM-FCD in the UV spectrum was also found to increase with the addition of Cu2+. The disappearance of the absorbance of Cu2+ itself suggest that coordination reaction between Cu2+ and PAMAM-FCD has occurred. These PAMAM-FCD dendrimers are promising to be the scarce material to emit blue fluorescence or as a dendrimer-copper hybrid material.

Compatibilization Effect of PTW on Polymer Blends of PA1010/PP

YANG Feng-Xia1,2, DU Rong-Ni2, LUO Feng2, ZHANG Xin-Lan2, YANG Jing-Hui2, FU Qia

2010, 31(1):  186-192. 

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In order to improve the compatibility and the mechanical properties of Polyamide1010 and Polypropylene(PA1010/PP)blends, a novel reactive compatibilizer ethylene-butylacrylate-glycidyl methacrylate terpolymer(PTW) was used to compatibilize the blends. The compatibilizing effect of PTW on PA1010/PP blends was investigated by means of scaning electron microscopy(SEM), Fourier transform infrared(FTIR),mechanical testing and differential scaning calorimetry(DSC), respectively. It was found that with increasing the PTW content, the size of the dispersed PP particles decreased obviously, when the mass ratio of PA1010/PP/PTW is 70∶30∶7, the domain size showed a fine and uniform dispersion in the matrix,indicated PTW had an effective compatibilization effect on PA1010/PP blends. FTIR results show that the epoxy groups of PTW react with the end group of PA1010 in the blending process. DSC results show that the addition of PTW decreased the crystallization temperature of PA1010, indicate that PTW has an inhibition effect on the crystallization of PA1010. On the other hand, with increasing the mass fraction of PTW content, the crystallization temperature of PP became lower too, when the mass fraction of PTW was 5%, two crystalline peaks appeared, the crystallization of PP at the lower temperature should be assigned to homogeneous nucleation, the other one was heterogeneous nucleation. The appearance of howogennous nucleation demonstrated that the size of PP particles was very fine in the matrix from the other hand. When the mass fraction of PTW was 7%, the blend had the best comprehensive property and the izod impact strength of dried samples was 13.93 kJ/m2 , which is 2 times that for the binary PA1010/PP blend. Meanwhile, the flexural strength, tensile strength and modulus can be maintained at a relative high level. The compatibilization mechanism of PTW lied in the chemical interactions occuring between the end group of PA1010 and epoxy groups of PTW during the blending process, and the compatibility between PP and ethylene groups of PTW. And hense the addition of PTW decreased the interfacial tension and the domain size dramatically, improved the mechanical properties greatly.

Adsorption Study of Gallic Acid by Hyper Cross-linked Resin Modified by Amino Function Groups

WANG Jin-Nan1,2*, XU Li1,2, LI Ai-min1,2*, ZHOU Yang1,2, XU Ling1,2

2010, 31(1):  193-198. 

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As typical natural organic acid of hydrophilicity and small molecule, gallic acid(GA) serves to study the adsorption act and mechanism on a new hyper cross-linked resin modified by amino function groups. The adsorption isotherm data indicates that WJN-10 show higher adsorption force and amounts of gallic acid than that of other adsorbents. Its absorption was characterized by physical absorption. Batch kinetic studies indicate that the adsorption of GA on WJN-10 could only be fitted by intra-particle diffusion model, and the intra-particle diffusion played a dominant role in the adsorption of GA. In particular, excellent adsorption and desorption performance of WJN-10 for gallic acid was shown in dynamic column assay.

Molecular Dynamics Simulation and Static Properties of Flexible Dendrimers in Solution

ZHANG Guo-Liang1,2, LU Yu-Yuan1, SONG Jian-Hui1,2, SHI Tong-Fei1*

2010, 31(1):  199-204. 

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We have performed molecular dynamics simulation to study the structural and dynamic properties of flexible dendrimers in athermal solvent. For dendrimers′ size, simulation results show that radius of gyration Rg can be fitted by the scaling law Rg~N1/5(G+1)2/5P2/5. As the generation number increases, the calculated static structure factor approaches that of hard sphere, which reflects a transition of internal structure from “starlike” to “hard-sphere-like” conformation. As dendrimers′ generation number and spacer length increase, there exists the distinct region, in which monomer density is almost constant. The back-folding ability of the dendrimers increases as spacer length increases but decreases as generation number increases. Each shell of dendrimers has different mobility. Compared with the interior of dendrimers, the outer shells show slower diffusion behavior within a shorter time but faster relaxation. The monomer motions exhibit a scaling that is much closer to Zimm than Rouse exponents.

Synthesis and Characterization of Anticoagulant Heparinized ε-Caprolactone/L-Lactide Copolymers and Their Electrospinning Study

GENG Xue1, YE Lin1, CHEN Bin2, WANG Pei-Jing1, ZHANG Ai-Ying1, ZHANG Jian2, FENG

2010, 31(1):  205-211. 

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Heparin-conjugated biodegradable copolymers were synthesized by attaching heparin to the ends of the copolyesters of ε-caprolactone and L-lactide(PLCL) in the presence of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide. They were characterized by means of 1H NMR, FTIR, XPS and UV-spectrophotometer techniques. The results indicate that heparin is successfully covalently coupled to PLCL, and the heparin-conjugated content is increased with increasing the ε-caprolactone molar content in the copolyesters. The PLCL surface after heparining became more hydrophilic than before due to the decrease of hydrophilic static contact angle. The clotting time of PLCL containing heparin was evaluated by activated partial thromboplastin time(APTT), thrombin time(TT) and prothrombin time(PT) measurements. The antithrombincity of the copolymers modified with heparin was improved among which the sample LC-90-H was the best. Finally, ultrafine fibers of LC-90-H were prepared by electrospinning process. It shows the promise to be applied in the inner-layer of tissue engineering blood vessel scaffolds.

Letters

Synthesis and Characterization of Novel Polyetherimide Contained Naphthalene Structure

LI Peng, CHEN Chun-Hai, WANG Dong-Ji, ZHOU Hong-Wei, ZHAO Xiao-Gang, DANG Guo-Do

2010, 31(1):  212-214. 

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A novel dichioro-monomer 4, 4′-bis(N-′phenyl-4-chloro-1,8-naphthalimide) ether(BCNPI) was successfully prepared. We obtain novel polyethernaphthalimide(PENI) from BCNPI and Bisphenol A salt in the present of sulfolane. The polymer possess high molecular weight from test of intrinsic viscosity and high Tg from the differential scanning calorimetry. The polyetherimide exhibited excellent thermal and thermooxidative stabilities, and it has high modulus, strength and elongation from the test of the mechanical properties.