Chem. J. Chinese Universities

Cover and Content of Chemical Journal of Chinese Universities Vol.33 No.1(2012)

2012, 33(01): 0-0.

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Research Progress on the Synthesis of Pillar[n]arenes and Their Host-guest Chemistry

WANG Kai, YANG Ying-Wei, ZHANG Sean Xiao-An

2012, 33(01): 1-13. doi:10.3969/j.issn.0251-0790.2012.01.001

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Pillararenes are a new class of host molecules, which are cyclic oligomers consisting of hydroquinones or 1,4-disubstituted hydroquinone ethers linked by methylene bridges in the para positions of the benze rings. Herein, recent development on the synthesis of pillar[n]arenes and pillar[n]arene derivatives, and their host-guest chemistry, i.e., molecular recognition and selective binding towards guest molecules, and their self-assembly properties was reviewed. In addition, prospects for future research based on pillar[n]arenes were also discussed.

Synthesis, Crystal Structure, Antibacterial Activity and Interaction with BSA of Copper(Ⅱ) Complex with Ligand N,N'-Bis(4-chlorobenzyl)propane-1,2-diamine

YANG Shu-Ping, HAN Li-Jun, PAN Yan, WANG Da-Qi, ZHAO Cui, WANG Bo

2012, 33(01): 14-21. doi:10.3969/j.issn.0251-0790.2012.01.002

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A new copper(Ⅱ) complex with ligand N,N'-bis(4-chlorobenzyl)propane-1,2-diamine, ·NH₄·Cl₂, has been synthesized and characterized by elemental analysis, IR spectra and single crystal X-ray diffraction methods. The crystal of copper(Ⅱ) complex belongs to triclinic system with space group P1, a=1.35222(16)nm, b=1.37899(17)nm, c=1.39806(19)nm; α=60.954(1)°, β=87.502(2)°, γ=65.970(1)°, V=2.0424(4) nm³, D_c=1.357 g/cm³, Z=2, F(000)=862, R₁=0.0925, wR₂=0.2668, S=1.001. The copper(Ⅱ) atom of the metal center in complex is five-coordinated by four N atoms from two ligand molecules and a terminal Cl atom, and the coordination polyhedron around the Cu atom can be described as a slightly distorted square pyramid-geometry with a distortion index τ value of 0.04(1). The complex exhibited good antibacterial properties and the interaction of complex and bovine serum albumin(BSA) was investigated by fluorescence spectroscopy at different temperatures. The results indicated that the complex caused the fluorescence quenching of BSA through a static quenching procedure. The binding constants(K_a), the number of binding sites(n≈1), and corresponding thermodynamic parameters enthalpy change(ΔH＞0), entropy change(ΔS＞0), Gibbs free energy change(ΔG＜0), between complex and BSA at different temperatures were calculated. The primary binding pattern between complex and BSA was interpreted as hydrophobic interaction. The binding average distance r between the donor(BSA) and acceptor(complex) was obtained to be 2.56 nm based on the Föster's theory, which indicates the energy transfer can occur from BSA to complex with high probability.

Synthesis and Characterization of Poly(ethylene glycol)/hydroxyapatite Hybrid Nanomaterials

ZHANG Peng, YANG Zhao-Yu, QIU Shu-Xuan, DING Ke-Yi, LUO Jian-Bin, XIE Xing-Yi

2012, 33(01): 22-25. doi:10.3969/j.issn.0251-0790.2012.01.003

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Poly(ethylene glycol ether) phosphate(P-MPEG) was synthesized through phosphorylating and hydrolyzing using poly(ethylene glycol methyl ether)(MPEG) as raw material. Then hybrid material with nHA core and polymer shell was synthesized through precipitation with P-MPEG as the steric hindrance agent. The nHA was characterized by Fourier transform infrared spectroscopy(FTIR), X-ray diffraction(XRD), transmission electron microscopy(TEM) and laser particle size analyzer(LPSA). The synthesized hybrid material is redispersible not only in water, but also in organic solvents such as methanol, N,N-dimethylformamide(DMF), etc. Feasibility of nHA with excellent redispersible ability using organic phosphate as the steric hindrance agent was confirmed.

Loaded and in vitro Drug Release of Anticancer Drugs in Porous Metal-Organic Frameworks

YANG Bao-Chun, JIANG Yao-Dong, QIN Xue-Juan, CHEN Zhi-Liang, REN Fei

2012, 33(01): 26-31. doi:10.3969/j.issn.0251-0790.2012.01.004

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Porous metal-organic frameworks(MOF-5) were synthesized and the structure of synthetic MOF-5 was confirmed by XRD and IR spectrum. According to the result of TG, the synthetic MOF-5 displayed better thermo-stabilization. The capsaicin or 5-fluouourail was loaded in synthetic MOF-5 and in vitro drug release profile were investigated, respectively. The highest drug loading rates are 0.592 g/g MOF for capsaicin and 0.315 g/g MOF for 5-FU in drug-loaded MOF-5, respectively. The in vitro drug release profile of both MOF-5 formulations showed a clear biphasic release pattern. Cytotoxicity test showed that MOF-5 displayed good biocompatility.

Effect of ZrOCl₂ Doping on Proton Conductive Performances of the Phosphosilicate Gels

HU Lin-Na, PENG Hui-Fen, HE Jun-Hua, AN Li-Yuan, GAO Chang-Hong

2012, 33(01): 32-36. doi:10.3969/j.issn.0251-0790.2012.01.005

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Effect of ZrOCl₂·8H₂O doping on proton conductive properties of phosphosilicate gel was investigated by means of sol-gel method. The results prove that ZrOCl₂·8H₂O can increase proton conductivity of the gel, and that the sample with ZrOCl₂·8H₂O content of 0.97%(mass fraction) shows maximum proton conductivity of 2.38 S/m at 130 ℃. The doped samples, on which no H₃PO₄ were found to precipitate during storage under a condition of R.H.(relative humidity) 40% for a month, exhibited no apparent changes in proton conductive performances. NMR measurements revealed that introduction of ZrOCl₂ to the gel could decrease the formation of isolated PO^3-₄ structural units and increase cross-linking between and tetrahedrons, thus resulted in an increase in both proton conductivity and chemical stability.

Carbon Nanotubes Assisted Solid-phase Extraction Combined with Dispersive Liquid-liquid Microextraction Based on Solidification of Floating Organic Droplet Method for the Determination of Trace Level Environmental Estrogens in Aqueous Solutions

LIU Jian-Lin, ZHANG Chen, WANG Xia-Jiao, WANG Ting, LI Yu

2012, 33(01): 37-43. doi:10.3969/j.issn.0251-0790.2012.01.006

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An analytical method, carbon nanotubes assisted solid-phase extraction combined with dispersive liquid-liquid microextration based on solidification of floating organic droplet(SPE/CNT-DLLME/SFO), was developed to determine estriol(E3), bisphenol A(BPA), 17α-ethinyl estradiol(EE2) and 17β-estradiol(E2) in aqueous samples. Both solid-phase extraction and dispersive liquid-liquid microextraction were investigated and optimized using central composite design, and the optimized conditions were obtained as follow: carbon nanotubes 30 mg, water sample 210 mL, flow rate of water sample 2.0 mL/min, extractant volume(dodecanol) 50 μL, dispersant(methanol) volume 0.2 mL, and without the addition of salts. Under the selected extraction conditions, linearity range of this established method were in the range of 0.05-100 μg/L for E3 and BPA, 0.05-50 μg/L for EE2 and E2, and the correlation coefficients (R²) were 0.9993-0.9999. The limits of detection were ranged from 3.3 to 48.4 ng/L. The recoveries of estrogens under different spiked levels (0.40 and 4.00 μg/L) for E3, BPA, EE2 and E2 were 107.5%-120.8%, 92.5%-108.3%, 103.5%-121.0% and 102.5%-132.5%, and the relative deviations were 2.47%-13.28%, 1.73%-11.94%, 1.72%-8.36% and 3.54%-11.95%, respectively. The average of enrichment factor for E3, BPA, EE2 and E2 were 461, 1075, 2074 and 949, respectively. Additionally, the established method could be applied to the analysis of estrogenic hormones in water samples collected from tap water, barrel-drain and commercial mineral water. Though it needs long time for solid phase extraction and large volume sample, compared with some other methods, the present method has many advantages such as low limit of detection which is on the same level as GC/MS(gas chromatography/mass spectrometry), high enrichment factor, simplicity of operation, low cost, and therefore it is an alternative method that could be widely used for the analysis of trace level of environmental estrogens.

New Fingerprinting Method Based on the Distribution of Nucleoside Compounds for Marine Animal Drugs by HILIC-ESI-TOF/MS

ZHAO Heng-Qiang, CHEN Jun-Hui, SHI Qian, LI Xin, CAO Wei, LI Jing-Xi, WANG Xiao-Ru

2012, 33(01): 44-48. doi:10.3969/j.issn.0251-0790.2012.01.007

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The feasibility of identification of the authenticity for various marine animal drugs was investigated by a fingerprinting method based on the distribution of nucleoside compounds, and a new method for the discrimination of precious animal drugs was provided. Sixteen nucleoside compounds in various marine animal drugs were determined by hydrophilic interaction liguid chromatography-electrospray ionization-time of flight-mass spectrometry(HILIC-ESI-TOF/MS). Characteristic fingerprint based on the distribution of 16 nucleosides was constructed, and it was used for identification of the authenticity of various marine animal drugs combined with similarity analysis and clustering analysis. The results indicated that the proposed characteristic fingerprint could reflect the inherent characteristics of their own for various marine animal drugs. Furthermore, it could be used to distinguish different marine animal drugs combined with similarity analysis and clustering analysis. In conclusion, the developed fingerprinting method is expected to be a powerful tool for the identification of animal drugs.

Microfluidic Cell Chip Analytical System with LED Induced Fluorescence Detector

LI Dong-Shun, XU Yi, PENG Jin-Lan, ZHOU Zhen, GAN Jun, WANG Yao

2012, 33(01): 49-53. doi:10.3969/j.issn.0251-0790.2012.01.008

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Based on micro-electro-mechanical systems technique and microfluidic cell chip analytical metho-dology, a microfluidic cell chip analytical system with light emitting diode(LED) induced fluorescence detector was constructed for monitoring cells in the suspensions with a low concentration below 40 Cell/mL. Cells passed through the micro-channels on the designed microchip, and the target cells labeled by 5- or 6-(N-succinimidyloxycarbonyl)-3',6'-O,O'-diacetylfluorescein(CFDA SE) were stimulated by the LED to produce fluorescence signals which were collected by a photomultiplier tube from the roof window and changed into electrical signals finally. The HepG2 hepatoma cells labeled by CFDA SE in samples could be detected and counted by this analytical microsystem. The designed microsystem ran effectively with the coexistence of blood cells. The whole microsystem is simple, convenient and high sensitivity.

Specific Assay of Amino Acids Based on a Fluorescent Conjugated Polyelectrolyte with Multi-carboxylates

FAN Hong-Liang, ZHANG Tao, LI Zu-Hong, WU Li-Yuan, JIN Qin-Han

2012, 33(01): 54-58. doi:10.3969/j.issn.0251-0790.2012.01.009

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A simple assay for cysteine(Cys) and histidine(His) based on a conjugated polyelectrolyte with multi-carboxylate groups was developed. The proposed approach takes advantage of the emission quenching of PPE-(COOK)₄ caused by Cu²⁺, which can be efficiently restored in the presence of Cys or His. Thus, the rapid assay of both amino acids can be carried out by measuring the fluorescence recovery. With the high similarity between the polymer’s side groups and EDTA, PPE-(COOK)₄ in phosphate buffer solution exhibits not only high sensitivity but remarkable specificity towards Cu²⁺, which makes it possible to introduce various shielding metals for improving the selectivity of Cys and His assays. The results demonstrated that both Cys and His can be assayed sensitively and selectively by adding Ni²⁺ or Hg²⁺ to PPE-(COOK)₄/Cu²⁺ system. The limit of detection is 0.15 μmol/L for Cys and 0.04 μmol/L for His, with the linear range of 1-5 μmol/L and 0.5-2.5 μmol/L, respectively.

Proteins Fluorescence Quenching by [Hg(SCN)₄]^2- and Its Analytical Application

TIAN Lun-Fu, LIU Zhong-Fang, HU Xiao-Li, KONG Ling, LIU Shao-Pu

2012, 33(01): 59-65. doi:10.3969/j.issn.0251-0790.2012.01.010

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[Hg(SCN)₄]^2- in acidic medium of pH=1.4-3.4 could react with proteins, including bovine serum albumin(BSA), γ-globin(γ-G) and hemoglobin(Hb), to form complexes. As a result, the fluorescence intensities of the proteins were significantly quenched. The quenched fluorescence intensities(ΔF) in a certain range were linearly related to the concentration of Hg(Ⅱ), and the detection limit(3σ) were 4.4 ng/mL(BSA), 6.5 ng/mL(γ-G) and 12.9 ng/mL(Hb), respectively. The effects of the interaction on the fluorescence spectral characteristics of these complexes, suitable reaction conditions and influencing factors were investigated. The quenching mechanism was studied by absorption spectroscopy, binding constant and corresponding thermodynamic parameters at different temperatures. Some potential interferents on the assay by BSA were investigated. The method displayed good selectivity and was satisfactorily applied to the determination of asceptichrome in mercurochrome solution and thiomersalatum in HB-vaccine.

Synthesis of Benzaldehyde and Succinic Acid by Paired Electrosynthesis with On-line Ultrasound

LI Yan-Wei, JIANG Guang-Ce, ZHANG Chuan-Guang, WEI Wen-Long

2012, 33(01): 66-70. doi:10.3969/j.issn.0251-0790.2012.01.011

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In the electrolytic process of out-cell indirect electrosynthesis of benzaldehyde, electrolytic yield of electrooxidating Ce³⁺ to Ce⁴⁺ in an undivided electrolytic cell was lower, while in diaphragm electrolytic cell would cause a high energy consumption. Based on this, a research with a combination of indirect electrosynthesis benzaldehyde and direct electroreduction maleic acid to succinic acid was carried out, and a new paired electrosynthesis system was constructed, that was, ion membrane paired electrolysis for preparations of Ce⁴⁺ on PbO₂/Pb anode coupling with succinic acid on Pb cathode using sulfuric acid solution as medium under ultrasonic radiation, then oxidizing toluene to benzaldehyde with the Ce⁴⁺ solution prepared in the first step. Experimental results showed that the synthesis of benzaldehyde and succinic acid by paired electrosynthesis with on-line ultrasound was feasible, and a high current efficiency could be obtained in both cathode and anode, which was 92.71% and 87.81% in average, respectively. Thus the total current efficiency was up to 180.52%. The percent conversion of maleic acid reached 92.09%, and the bath potential decreased 0.25 V. Besides, a good result was also obtained in oxidating toluene to benzaldehyde using the Ce⁴⁺ solution with on-line ultrasound, the yield of benzaldehyde was 95.78% in average.

Highly Efficient Synthesis of Two Globo H Tetrasaccharide Analogues

WEI Guo-Hua, DU Yu-Guo

2012, 33(01): 71-75. doi:10.3969/j.issn.0251-0790.2012.01.012

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The synthesis of two Globo H tetrasaccharide analogues, allyl O-(β-D-glucopyranosyluronic acid)-(1,3)-O-(β-D-galactopyranosyl)-(1,3)-(2-acetamido-2-deoxy-β-D-galactopyranosyl)-(1,3)-O-α-D-galactopyranoside and allyl O-(3-O-sulfo-β-D-glucopyranosyluronic acid)-(1,3)-O-(β-D-galactopyranosyl)-(1,3)-(2-acetamido-2-deoxy-β-D-galactopyranosyl)-(1,3)-O-α-D-galactopyranoside, were described. Construction of the target molecules was achieved through a key combination of BF3·Et2O and trichloroacetimidate glycosylation methodology. This is the first report on the synthesis of these derivatives, which could be used as potential novel substrates and reference samples for the study of β1,3-glucuronosyltransferase and GlcA-3-O-sulfotransferase in cancer tissues.

Synthesis of Functionalized Ionic Liquids Based on Benzimidazolium and Their Properties

WANG Bin, LIU Chen-Jiang, WANG Ji-De, LEI Zhen-Kai, HU Dong-Lin

2012, 33(01): 76-81. doi:10.3969/j.issn.0251-0790.2012.01.013

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A series of functionalized ionic liquids based on benzimidazolium cation was synthesized and cha-racterized by ¹H NMR, ¹³C NMR, IR and ESI-MS. The thermal stability, electrical conductivity, the solubility in various solvents and other properties were studied. The results showed that the ionic liquids had no weight loss under 280 ℃, indicating they have a good thermal stability. When the concentration of the ionic liquids in the aqueous solution is 1×10^-3 mol/L, increasing the conductivity is almost proportional to the temperature increases, miscible with most organic solvents, solubility with the increase of solvent polarity.

Synthesis and Optical Properties of 3D Compounds with Core and D-π-A Dipolar Group

HU Bin, OUYANG Mi, ZHANG Yu-Jian, XIANG Wen-Qin, ZHANG Cheng

2012, 33(01): 82-89. doi:10.3969/j.issn.0251-0790.2012.01.014

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Four novel 3D compounds with core and donor-π-acceptor(D-π-A) ambipolar group were synthesized via Suzuki and Friedel-Crafts copolycondensation reaction and charactered by NMR, MS, TGA, DSC and absorption and emission spectrometry. The results indicated that introduction of the cores could efficiently retard the crystallization tendencies of the D-π-A structure and gave the materials completely amorphous morphological structure. As a result of the coexistence of the electron acceptor and donor, these compounds diaplayed reversible electrochemical behavior. All the compounds showed better stability of thermal and electrochemical. The mitigation of aggregation in solid-state were observed by comparing the optical properties of the films between compounds 1—3 and linear counterparts. Four compounds exhibited bathochromism in different solvents due to the intromolecular charge transfer(ICT). With the changing of the polarity of solvent and the strength of the electron acceptor, the optical properties of compounds could be modified, and the PL intensity of compounds was also tailored with the difference of solvent.

Blood Compatibility Improvement of Titanium via Self-polymerization of Dopamine and Covalent Graft of Heparin

XIE Bing, LI Gui-Cai, DAI Lu, YANG Ping, HUANG Nan

2012, 33(01): 90-95. doi:10.3969/j.issn.0251-0790.2012.01.015

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Self-polymerization of dopamine and immobilization of heparin were applied for surface-modification of titanium in order to improve its blood compatibility. Surface modification was developed via self-polymerization of dopamine and covalent graft of heparin. Surface elemental composition was analyzed qualitatively by X-ray photoelectron spectroscopy(XPS). Surface heparin content was detected by toluidine blue O(TBO). Surface hydrophilicity and hydrophobicity were characterized by water contact angle measurement. Hemolysis rate test, which was applied for detection ofhemolytic ability, was combined with activated partial thromboplastin time test(APTT) and platelet adhesion test to evaluate blood compatibility. The results showed that self-polymerization of dopamine was achieved on titanium surface. Heparin was successfully immobilized onto polydopamine layer by covalent graft. The heparin-modified surface could result in a significantly improved hydrophilicity, low hemolysis rate, prolonged APTT and a remarkablely decrease both in adhesion amount and activation degree of platelet. The blood compatibility of titanium could be significantly improved by the method of self-polymerization of dopamine and covalent graft of heparin. This study provides potential application for cardiovascular implants materials with anticoagulant properties.

Oxidative Dehydrogenation of Propane to Propylene with CO₂ over Cr/NaZSM-5 Catalysts

ZHANG Fan, NIE Ying-Ying, MIAO Chang-Xi, YUE Ying-Hong, HUA Wei-Ming, GAO Zi

2012, 33(01): 96-101. doi:10.3969/j.issn.0251-0790.2012.01.016

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A series of Cr catalysts supported on submicro NaZSM-5 zeolite was prepared. The obtained samples were characterized by N₂ adsorption, XRD, UV-Vis and H₂-TPR, and tested as catalysts for dehydroge-nation of propane to propylene in the presence of CO₂. The highest activity was achieved on the catalyst with a Cr content of 3% and a Si/Al molar ratio of 60. In this case, the propane conversion and propylene selectivity were 48.3%, 86.0% and 30.1%, 91.8%, respectively after the reaction at 550 ℃ for 10 min and 8 h. There is a good relationship between the initial activity and Cr⁶⁺ content of the catalysts, showing that a high content of Cr⁶⁺ species in the calcined catalyst is crucial for its high catalytic activity in dehydrogenation of propane to propylene with CO₂. A higher propylene yield was obtained during propane dehydrogentaion in the presence of CO₂ than N₂. This can be attributed to a higher surface concentration of Cr⁶⁺ retained on the catalyst in the presence of CO₂ as well as the elimination of hydrogen produced by propane dehydrogenation.

Electrocatalytic Performance of Graphene Supported Ir Catalyst for Ammonia Oxidation

LI Lin-Ru, FU Hong-Gang, LU Tian-Hong

2012, 33(01): 102-106. doi:10.3969/j.issn.0251-0790.2012.01.017

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Instead Vulcan XC-72 carbon(XC), grapheme(G) was used as the support to prepare the Ir/G catalyst. The electrochemical measurement indicted that the electrocatalytic performance of the Ir/G catalyst for the ammonia oxidation was better than that of the Ir/XC catalyst. XRD and TEM measurements indicated that the average sizes of Ir particles in Ir/G and Ir/XC catalysts were similar. The measurement of the Raman spectroscopy illustrates the graphitization extent of G is higher than that of XC. Thus, the conductivity of G is higher than that of XC. Therefore, the electrocatalytic performance of the Ir/G catalyst is better than that of the Ir/XC catalyst can be attributed to the high conductivity due to the high graphitization extent of G. The results show that there is the good linear relationship between the current density of the ammonia oxidation at the Ir/G catalyst electrode and the concentration of ammonia. The related coefficient(R) is 0.99557. Thus, Ir/G catalyst electrode can be used as the working electrode in the current type of electrochemical ammonia sensor.

Synthesis of Carboxyl-functionalized Silica Coated Fe₃O₄ Magnetic Nanoparticles and Their Adsorption Ability of Cu²⁺

ZHENG Qun-Xiong, LIU Huang, XU Xiao-Qiang, DU Mei-Xia

2012, 33(01): 107-113. doi:10.3969/j.issn.0251-0790.2012.01.018

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Carboxyl-functionalized Fe₃O₄ magnetic nanoparticles(CMNP) with core-shell structure were prepared by modifying silica coated Fe₃O₄ magentic nanoparticles(MNP), which were successfully prepared by co-precipitation method, with 3-aminopropyltriethoxysilane(APTES) and Succinic anhydride. The morphology, structure, chemical composition and magnetic characteristics of the CMNP were characterized by transmission electron microscopy(TEM), X-ray diffraction(XRD), X-ray energy dispersive spectroscopy(EDS), vibrating sample magnetometer(VSM), thermal gravimetric analysis(TGA) and Fourier-transformed infrared spectroscopy(FTIR). Moreover, the adsorption properties of the CMNP for the removal of Cu²⁺ in aqueous solution were investigated and various factors affecting the absorption behavior of Cu²⁺ such as initial pH value, initial concentration of Cu²⁺ and contact time were studied. The TEM results show that the average partical size of CMNP is 15 nm. Magnetic measurement reveals it is nearly superparamagnetic with a saturation magnetization of 41.84 A·m²/kg. Adsorption equilibrium was achieved rapidly in 10 min and adsorption data of CMNP fitted well with the Langmuir isotherm model with the maximum adsorption capacity of 43.48 mg/g, the maximum uptake of Cu²⁺ was recorded at pH=7.

Determination of Osmotic Coefficients and Representation with Ion-interaction Model for NaOH-NaAl(OH)₄-H₂O System at 303.15 K

SONG Ting, LIU Shi-Jun, XIAO Liu-Ping, CHEN Qi-Yuan

2012, 33(01): 114-118. doi:10.3969/j.issn.0251-0790.2012.01.019

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The isopiestic equilibrium molalities and the osmotic coefficients for the NaOH-NaAl(OH)₄-H₂O system were measured using isopiestic method. At 303.15 K with the total alkli molality from 0.61 mol/kg to 5.72 mol/kg and molar ratio of Na₂O to Al₂O₃(α_K) from 1.98 to 7.04. The experimental data were represented by the Pitzer model. The Pitzer ion interaction parameters were evaluated from experimental data using multiple regression. The measured data of osmotic coefficients are in reasonable agreements with those calculated by the model. The activity coefficients of NaOH and NaAl(OH)₄ in the system were calculated from the ion interaction model parameterized, and the values increased with the total alkli molality increasing. These studies are useful to improve the thermodynamic model for sodium aluminate solutions systems and sodium aluminosilicate solutions systems.

Ion Exchange Reaction Kinetics of Magnetic Layered Double Hydroxides with 5-Fluorouracil

GOU Guo-Jing, LIU Yan-Hong, SUN Yue, HUANG Jie, XUE Bing

2012, 33(01): 119-127. doi:10.3969/j.issn.0251-0790.2012.01.020

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Using the magnetic layered double hydroxides(MLDH) synthesized by co-precipitation as a precursor, the dynamic feature of ion exchange reaction between MLDH and fluorouracil(FU) under the condition of 0-50 ℃ was investigated via the liquid data fitting and solid-phase characterization of MLDH-fluorouracil in situ reaction system. The results show that MLDH and product MLDH-FU belonged principally to a six square crystal series(R-space group) are magnetic compound crystal phase mixed trace iron oxide. The ion exchange rate of MLDH-FU increases significantly with the increase of temperature, and the concentrations varying of three object FU, OH^- and Cl^-, respectively, obey the secondary reaction, zero-order reaction and first-order reaction rate models, the reaction activation energy are 12.69, 27.88 and 3.580 kJ/mol, respectively. Cha-racterization parameters of solid-phase samples change with the liquid kinetic process, object structure adjustment and particle development process of MLDH-FU. Ion exchange limited within interval of LDH layers dones’t affect the internal structure order of layers, and doesn’t change the structure and layered morphology characteristics of precursor, with a non-break-layer reaction behavior. The ion exchange reaction between MLDH and FU is an orderly process started from the absorption affinity of exchange agent FU in MLDH peripheral, lateral offensive, interlayer displacement, and transformation in pillared model to a structure adjustment leaded by the new intercalated object, and grain development process.

Effects of Electrolyte Solutions on Overoxidation of Polypyrrole During Its Electrochemical Polymerization

LI Mei-Chao, ZHU Wan-Xia, ZHU Jing-Na, MO Wei-Min

2012, 33(01): 128-132. doi:10.3969/j.issn.0251-0790.2012.01.021

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Polypyrrole(PPy) was prepared by cyclic voltammetry on a platinum electrode in H₂SO₄/H₂O and LiClO₄/CH₃CN solutions, respectively. The effects of electrolyte solutions on overoxidation of polypyrrole during its electrochemical polymerization were studied by in situ spectroelectrochemical measurements. Compared with the solution of H₂SO₄/H₂O, the overoxidative peak potential of polypyrrole in LiClO₄/CH₃CN was positively shifted by 0.42 V. The results show that the β-C of the pentacycle is oxidized to oxygen-containing groups such as C—OH and CO during the overoxidation of polypyrrole at high potentials. Polypyrrole partially degraded with the formation of CO₂ in H₂SO₄/H₂O solutions, which resulted in loss of conductivity, and did not obviously degrade during overoxidation in the solution LiClO₄/CH₃CN at the higher potentials.

In-situ Synthesis of Pt Nanoparticles on Graphene Nanosheets and Its Electrocatalysis for the Oxygen Reduction Reaction

HE Wei, ZOU Liang-Liang, ZHOU Yi, LU Xiang-Jun, LI Yuan, ZHANG Xiao-Gang, YANG Hui

2012, 33(01): 133-138. doi:10.3969/j.issn.0251-0790.2012.01.022

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Pt nanoparticles were anchored on graphene nanosheets(GNs) with the aid of poly(diallyldime-thylammonium chloride) (PDDA). The Pt ions were assembled first onto PPDA-modified graphene oxide nanosheets and then the caged Pt ions and graphene oxide were reduced simultaneously by ethylene glycol. As was supported by transmission electron microscopy, Pt nanoparticles were well-dispersed on GNs. Comparing with the commercial Pt/C and Pt/GNs(without PDDA) catalysts, the as-prepared Pt/PDDA-GNs nanohybrid exhibited an enhanced catalytic activity for the oxygen reduction reaction(ORR) and a significant improvement in the electrochemical durability. The enhanced durability could be ascribed to the increased Pt oxidation potential and to a strengthened metal-support interaction. The results show that PDDA plays an important role in the dispersion and stabilization of Pt nanoparticles on GNs, thus leading to an enhancement in both activity and durability of the catalyst for the ORR. This preparation procedure is effective and may be extended to synthesize other metal-graphene composites.

Surface-enhanced Raman Scattering of Molecules Adsorbed on SnO₂ Nanoparticles

HOU Jin-Long, JIA Xiang-Fei, XUE Xiang-Xin, CHEN Lei, SONG Wei, XU Wei-Qing, ZHAO Bing

2012, 33(01): 139-143. doi:10.3969/j.issn.0251-0790.2012.01.023

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Pure SnO₂ nanoparticles were prepared by the sol-hydrothermal method and were employed as surface-enhanced Raman scattering(SERS) active substrates. The relationships between defect levels and SERS effect of SnO₂ nanoparticles were mainly investigated. The strongest SERS signals were observed when the 4-mercaptobenzoic acid molecules were adsorbed on the surface of SnO₂ nanoparticles(hydrothermal pro-duct), with the increase of calcining temperature, the SERS signals became weaker. Transmission electron microscopy, UV-Vis diffuse reflectance spectroscopy, photoluminescence X-ray diffraction and X-ray photoelectron spectroscopy have been employed to investigate the SnO₂ nanoparticles. The results indicated that surface properties of SnO₂, such as surface defects and oxygen vacancies, etc, play important roles in the SERS. The higher is the content of surface defects and oxygen vacancies, the stronger is SERS signals.

Monte Carlo Simulation of the Radius of Gyration of Hyperbranched Polymers Formed in Self-condensing Vinyl Polymerization System in the Presence of Core Initiators with Unequal Reactivity

ZHENG Yue, WANG Hai-Jun

2012, 33(01): 144-148. doi:10.3969/j.issn.0251-0790.2012.01.024

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The second radius of gyration of hyperbranched polymers formed in self-condensing vinyl polymerization system in the presence of core initiators was studied by the method of Monte Carlo simulation, in which the unequal reactivity was taken into account. As a result, the roles of the reactivity differences in two types of active groups, the molar ratio and functionality of core initiators were mainly discussed, and it was found that these factors could give rise to a significant influence on the radius of gyration of hyperbranched polymers with and without a core initiator. This provides some useful clues for regulating the dimension of the hyperbranched polymers in the relevant experiments.

Nonlinear Optical Properties of Silver Nanocrystals with Different Shapes

WANG Rui, PAN Ling-Yun, XIA Xiao-Dong, HAN Dan-Ao, YANG Han

2012, 33(01): 149-152. doi:10.3969/j.issn.0251-0790.2012.01.025

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Silver nanocrystals with prism and disk shapes have been synthesized by the light-driven growth method in an aqueous solution. Nonlinear optical properties of these two samples were investigated by home-built femtosecond Z-scan system with 800 nm incident wavelength. The Ag nanoprisms with 75 nm size show 700 nm SPR peak and exhibit both negative and positive nonlinear absorption. The nonlinear absorption process is considered to be generated by ground-state plasmon bleaching, free-carrier absorption, and interband transitions. The Ag nanodisks with 35 nm size show 495 nm SPR peak. However, Ag nanodisks display only positive nonlinear absorption process. The different nonlinear absorption process is attributed to the morphology influence by the Ag nanocrystals.

Conformational Analysis of Trandolapril in Solution by NMR

SHEN Li, JIANG Jin-Liang, YU Yi-Hua, WU Yan-Bo, SUN Xiu-Yan, GU Qian-Qun

2012, 33(01): 153-157. doi:10.3969/j.issn.0251-0790.2012.01.026

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Trandolapril, a potent inhibitor of angiotensin converting enzyme, was studied by nuclear magnetic resonance(NMR) spectroscopy. It was found that trandolapril had two conformations in CDCl₃, and conformer A could converted gradually into conformer B at room temperature. The two conformations of trandolapril were elucidated by NMR spectroscopy and in combination with structural simulation based on density function theory(DFT). The results show that the two conformers of trandolapril interchange via rotation about the amide bond, and the conformer B(cis) is the preferred conformation. The energy difference of two conformers is 6.35 kJ/mol.

Catalytic Performances of Co-Pd/TiO₂ Catalysts Prepared with Mixed Cobalt Salts for Acetic Acid Synthesis from CH₄ and CO₂ by a Step-wise Reaction Sequence

GAO Zhong-Liang, HUANG Wei, YIN Li-Hua, JI Peng, ZHAO Jin-Zhen, LIU Yuan, PENG Fen

2012, 33(01): 158-165. doi:10.3969/j.issn.0251-0790.2012.01.027

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Co-Pd/TiO₂ catalysts were prepared from mixed cobalt salts by incipient impregnation method. The catalytic performance of the catalysts for direct synthesis of acetic acid from CH₄ and CO₂ by a step-wise reaction technology was investigated. These catalysts were also characterized by XRD, XPS, NH₃-TPD and BET. The results show that when the precursor is from mixed cobalt salts, a suitable surface acidity, high specific surface area and pore structure are formed, which favors the activity of catalysts. On the condition of m(CoCl₂)∶m=2∶5, m(Co)∶m(Pd)=2∶1 and 150 ℃, the formation rate and selectivity of acetic acid reach 6.13 mg·g^-1Cat·h^-1and 81.6%, respectively. Compared with the catalysts prepared from single cobalt, the rate and selectivity increase by 134% and 16%.

Effects of pH on Secondary Structure and Orientation of the Transmembrane Domains of Slc11a1 in Lipid Membrane

LI Jian-Tao, QI Hai-Yan, LI Fei

2012, 33(01): 166-171. doi:10.3969/j.issn.0251-0790.2012.01.028

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Transmembrane protein Slc11a1(Solute carrier family 11 member 1) is a divalent metal ion transporter which includes 12 transmembrane domains(TMDs). In this paper, the secondary structure and orientation of the peptides corresponding to TMD2, TMD3 and TMD4 in the phospholipid vesicles[n(DMPC)∶n(DMPG)=2∶1] at different pH values were investigated by circular dichroism, fluorescence, polarized attenuated total reflection Fourier transform infrared spectroscopies and differential scanning calorimetry. It was found that the secondary structure and positioning of TMD3 in lipid membrane are dependent on solution pH. TMD3 folds mainly as a β strand and is embedded in lipid membrane less deeply at pH=7, while it forms part of α-helix and inserts more deeply in lipid membrane at pH=5.5. These were attributed to the acidic residue Glu139 of TMD3, as indicated by the results of the E139A mutation of TMD3. Both TMD2 and TMD4 form predominantly α-helix structure at different pH values and insert into lipid membrane by tilt angles of 26° and 35°, respectively, and the positioning of them in membrane is basically independent of pH.

Foaming Behavior of Compatible PMMA/[C₁₂ MIM][PF₆] System by Supercritical CO₂

TONG Fang-Fang, XU Hong, YU Jian, WEN Li-Xiong, ZHANG Jun, HE Jia-Song

2012, 33(01): 172-175. doi:10.3969/j.issn.0251-0790.2012.01.029

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A series of compatible blends of poly(methyl methacrylate) with an ionic liquid(IL), 1-dodecyl-3-methylimidazolium hexafluorophosphate[C₁₂ MIM][PF₆], was prepared by melt blending. The blends were foamed with supercritical CO₂ as the blowing agent via a rapid pressure-quenching process. By adding IL, the CO₂ absorption of PMMA was increased, and the glass transition temperature was lowered. The effects of IL on the foaming behavior of PMMA depended on foaming conditions. When the foaming temperature and pressure were low, pure PMMA could not be foamed, while the addition of IL facilitated the formation of cells. On the other hand, pure PMMA could be foamed at higher temperatures and pressures, and adding IL further increased the cell size of the foamed samples; however, the cell size was still within the micron-meter scale and had a narrow distribution.

Synthesis and Performance of PAMAM-Lys Dendrimer

GUO Ling-Xiang, GAO Qiu-Duan

2012, 33(01): 176-181. doi:10.3969/j.issn.0251-0790.2012.01.030

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L-Lysine was used to modify 4.0G polyamidoaminec(PAMAM), and a new polyamidoamine derivative named PAMAM-Lys was synthesized via the liquid-phase synthesis. The structures of PAMAM-Lys were characterized by IR, ¹H NMR, elementary analysis and granularmetric analysis. For PAMAM-Lys, the elemental analysis results of C, H and N were 53.43%, 9.58% and 24.29%, respectively, the end amino measured value was 2.18, close to the theoretical value. The mean grain size of PAMAM-Lys was about 6.35 nm and its particle size polydispersity was about 0.09. Microstructures of the composites were observed by TEM. The cytotoxicity tests in vitro transfected with PAMAM and PAMAM-Lys dendrimers were evaluated by Thiazolyl Blue Tetrazolium Bromide(MTT) assay. According to the observed results with TEM, the composite of PAMAM-Lys and plasmid DNA made the DNA structure shrink, the average grain diameter of plasmids ranged from 50 nm to 100 nm, plasmids had the even distribution and the regular morphology. On the basis of the MTT assay results, when acting on 293T in vitro, PAMAM-Lys and PAMAM-Lys/DNA had the lower cytotoxicity and the better biocompatibility than 5.0G PAMAM. It showed that PAMAM-Lys dendrimer had been synthesized successfully, the modification by lysine could reduce the cytotoxicity of PAMAM dendrimer significantly. PAMAM-Lys had the better biocompatibility in vitro and could improve the transfection efficiency for DNA, thus PAMAM-Lys would be a promising DNA vector in future.

Alkyl Chain Effect and Photoelectric Properties of D-A-D Structural Solution Processable Organic Small Molecules

LI Qiang, LIU Zhao-Yang, LIU Lei-Jing, LI Zai-Fang, CHENG Wei-Dong, LI Hui, LI Peng-Fei, LI Zi-Jian, GUAN Chang-Jian, JIA Yi-Long, TIAN Wen-Jing

2012, 33(01): 182-187. doi:10.3969/j.issn.0251-0790.2012.01.031

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Three novel solution processable organic small molecules, TPT-N, TPT-S and TPT-D with a Donor-Acceptor-Donor(D-A-D) structure based on thiophene donor unit and 2-pyran-4-ylidenemalononitrile(PM) acceptor unit, were designed and synthesized. Effect of alkyl chain number on the solubility, photophysical properties(absorption characteristic), thermal stability and photoelectric properties of the molecules were investigated. The results indicate that with the alkyl chain increasing the solubility and film-forming pro-perties of the molecules increase, and the absorption spectra of the organic small molecules are red-shifted in solutions and the absorption bands in films become narrow. Moreover, the highest occupied molecular orbital(HOMO) energy levels also increase with the alkyl chain of the molecules increasing. Bulk heterojunction structural solar cells with a device structure of ITO/PEDOT∶PSS/D-A-D∶PCBM/LiF/Al based on the D-A-D organic small molecules as the donor,(6,6)-phenyl C₆₁-butyric acid methyl ester(PCBM) as the acceptor were fabricated. It is found that the device based on TPT-S which has a single alkyl chain on the thiophene unit has a relatively high power conversion efficiency(PCE). The research results confirm that the alkyl chain number is one of the most important effects that influence the properties of the materials and device perfor-mance as for D-A-D organic small molecular solar cell materials.

Formation and Evolution of Raspberry-like Structures from Cardiolipin

CHEN Yan, LI Li, QIU Feng

2012, 33(01): 188-192. doi:10.3969/j.issn.0251-0790.2012.01.032

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Using confocal microscopy and optical microscopy, the formation and evolution of the self-assembly structures from cardiolipin were investigated in NaCl solutions. The results show that, as the solution concentration is close to physiological concentrations, micro-hemispherical cells emerge on the surface of sponge phase cardiolipin, which tend to automatically arrange in a honeycomb-like array. The slow increasing of the brine content in solutions would drive the phase transition from sponge phase to lamellar phase continuously developed toward to the deep-center of sponge phase cardiolipin. On the other hand, the pressure and shear stress from weak flowing of the fluid also can affect the final morphology of these micro-cells, make them appear as honeycomb-like structures, raspberry-like domes and raspberry spheres. Since cardiolipid plays an important role for mitochondrial function, we hope these above results on phase transition and morphology evolution may improve our understanding of the acting mechanisms of cardiolipin.

REDV/Peptide Conjugated Rapamycin-loaded Polymer Matrix for Endothelial Cells Selectivity

WEI Yu, JI Ying, JI Jian

2012, 33(01): 193-198. doi:10.3969/j.issn.0251-0790.2012.01.033

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Combination device containing drug release and HUVECs selectivity were constructed based on PEG copolymer. Polyethylene glycol methacrylate(PEGMA)-butyl methacrylate(BMA)(PEGB) loading rapamycin was cast onto polyethylene terephthalate(PET) substrate as base layer, and then PEGMA-BMA-p-nitrophenyloxycarbonyl polyethylene glycol methacrylate(MEONP)(PEGBN) conjugated REDV peptide was further coated as top layer. In vitro profile of drug release indicates that rapamycin keeps a slow and sustain release implying that the top layer acts as a diffusion barrier. Cell behavior indicates that rapamycin remains its activity in inhibiting human umbilical vein endothelial cells(HUVECs) and human aortic smooth muscle cells(HASMCs) adhesion and proliferation. Although the eluted concentration of rapamycin decreased with drug eluting time, the polymeric coating keeps resisting nonspecific adsorption of HASMCs while REDV enhances HUVECs attachment specifically. This polymeric film with top layer promotes HUVECs competitive adhesion comparing with HASMCs. The immobilization of REDV onto rapamycin loaded PEG matrix could be an effective method to keep sustained inhibition of HASMCs and promote HUVECs competitive adhesion simultaneously.

Mechanism of Graft Polymerization of Methyl Methacrylate-Acrylonitrile onto Poly(ethene-co-1-butene)

XIONG Kai, ZHU Yong-Ping, WANG Xia, WANG Lian-Shi, CAI Tong-Min, ZHANG An-Qiang, ZENG Xiang-Bin

2012, 33(01): 199-205. doi:10.3969/j.issn.0251-0790.2012.01.034

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The effects of reaction time on reaction behavior of suspension grafting copolymerization of methyl methacrylate(MMA)-acrylonitrile(AN) onto poly(ethene-co-1-butene)(PEB) and toughening effect of PEB-g-MAN on SAN resin were investigated. The grafting polymerization product was characterized by GPC and FTIR analysis, the grafting copolymerization mechanism was investigated and the formula of calculating molecular weight of grafted chain was established. The results show that firstly the polymerization is mainly forming non-grafted copolymer with low molecular weight(MAN_L) of the transferring terminating polymerization of chain propagating free radicals and forming the grafted chains(g-MAN) of the transferring graft polymerization, and then the polymerization is mainly forming non-grafted copolymer with high molecular weight(MAN_H) of bimolecular terminating polymerization of chain propagating free radicals; molecular weight of MAN_L is less than that of g-MAN and molecular weight of g-MAN is less than that of MAN_H; there exist chain scission and random regrafting of the backbone of PEB-g-MAN and ungrafted PEB which result in the production of multi-block polymer of PEB and PEB-g-MAN during the grafting copolymerization; mass fraction of AN unit in grafted chain is close to mass fraction of AN unit in non-grafted copolymer in the initial stage and the former is much less than the later in the later stage.

Preparation and Characterization of Solvent-free Fe₃O₄ Nanofluids

TAN Yu-Mo, ZHENG Ya-Ping, LAN Lan

2012, 33(01): 206-209. doi:10.3969/j.issn.0251-0790.2012.01.035

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The surfactant was used to functionalize the nanoparticles to prepare solvent-free nanofluids. To prevent Fe₃O₄ nanoparticles from agglomerating and improve the dispersion of Fe₃O₄ nanoparticles, the solvent-free Fe₃O₄ nanofluids were synthesized through surface modification. Magnetic Fe₃O₄ nanoparticles were firstly prepared by chemical co-precipitation method. Then graft the quaternary ammonium salt (CH₃O)₃Si(CH₂)₃N⁺(CH₃)₂(C₁₈H₃₇)Cl^-, which has silanol groups, on Fe₃O₄ nanoparticles with hydroxyl groups. Finally, the chloridion was replaced with the anion C₉H₁₉—C₆H₄(OCH₂CH₂)₂₀O(CH₂)₃SO₃ through an ion-exchang process. An organic layer was formed on the surface of Fe₃O₄ nanoparticles, and made the Fe₃O₄ nanoparticles from black powder to brown fluid(at room temperature). The solvent-free Fe₃O₄ nanofluids were characterized by X-ray diffraction, Fourier transform infrared spectrum, differential scanning calorimetry, thermogravimetric analysis, transmission electron microscopy and rheometer. The Fe₃O₄ nanoparticles were monodispersed in solvent-free nanofluids, and the content of Fe₃O₄ nanoparticles in the nanofluids proved to be about 12%. The loss shear modulus G″ was higher than the storage shear modulus G'.

Evaluation of the Cytotoxicity About Photic Organic Nanoparticles

LI Xiao-Dong, YANG Shu-Min, XU Hong, MA Yu-Guang

2012, 33(01): 210-214. doi:10.3969/j.issn.0251-0790.2012.01.036

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The cytotoxicity about organic nanoparticles which has the function of two-photon fluorescent probe 2,5,2',5'-tetra(4'-N,N-diphenylaminostyryl)biphenyl(DPA-TSB) was studied. The physiological activity of stomach cancer cells after englobing the nanoparticle was detected by the methods of WAT-1, Lactate dehydrogenase(LDH) and flow cytometry. The results show that the stomach cancer cells can live well when the concentration of the nanoparticles is below 12 μg/mL, which suggests that the nanoparticles have the property of good biological security.

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