Table of Content

10 March 2008, Volume 29 Issue 3

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高等学校化学学报2008年第29卷第3期目次

2008, 29(3):  0.  doi:

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下期目次预览

2008, 29(3):  0.  doi:

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研究论文

Synthesis and Characterization of Titanate and CS₂-modified Titanate Nanotubes as Well as Their Adsorption Capacities for Heavy Metal Ions

AN Hui-Qin, ZHU Bao-Lin, WU Hong-Yan, ZHANG Ming, WANG Shu-Rong, ZHANG Shou-Min, WU Shi-Hua, HUANG Wei-Ping*

2008, 29(3):  439-444.  doi:

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CS₂-modified titanate nanotubes were synthesized by tubular titanate precursor via hydrothermal method. They were characterized with XRD, EDAX, TEM and Raman spectra. Adsorption capacity of the nanotubes for heavy metal ions, such as Cu²⁺, Pb²⁺ and Ag⁺ ions in water were also evaluated. Compared with ordinary sorbents, the nanotubes’ adsorption performance are much better. The nanotubes’ adsorption capacities increase apparently after being modified by CS₂, and their adsorption performance is related to the anions and pH value of the solution. The adsorption capacities of pure titanate nanotubes for Pb²⁺, Ag⁺ and Cu²⁺ ions are 599.37, 163.22 and 474.73 mg/g, respectively. After being modified by CS₂, the adsorption capacities of the nanotubes changed to 663.37, 160.21 and 423.05 mg/g, respectively.

Synthesis of Metal Phthalocyanines Containing Piperidine and Their Photoinhibition on Cancer Cell

HUANG Zi-Yang^1,2, XUE Jin-Ping¹, CHEN Jin-Can³, CHEN Nai-Sheng¹, HUANG Jin-Ling¹*

2008, 29(3):  445-448.  doi:

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“The template approach” was used for the synthesis of eight metal phthalocyanine complexes containing piperidine group(PEO)₄PcM, where M=Zn, Ni, Co, Cu, PEO=2-(piperidin-1-yl) ethyoxyl. These complexes were characterized by FTIR, mass spectrum, elemental analysis and so on. The UV-Vis absorption spectra, fluorescence emission spectra and capacity of photo-generating singlet oxygen were examined. The results showed that two zinc phthalocyanine complexes possessed high molar extinction coefficient, fluorescence quantum yield, high rate of photo-generating singlet oxygen. The complex with formula β-(PEO)₄PcZn had a photoinhibition effect to BEL7402 liver cancer cells up to 83% in case that the irradiation with 670 nm laser light(dosage 1.2 J) and the concentration of β-(PEO)₄PcZn with 10 μmol/L were used.

Hydrothermal Synthesis, Crystal Structure, Luminescence and Electrochemical Properties of Trinuclear Zinc(Ⅱ) Complex Zn₃(phen)₂(2,4-DAA)₆

YANG Ying-Qun¹, LI Chang-Hong², LI Wei¹*, LI Dong-Ping³, KUANG Yun-Fei¹

2008, 29(3):  449-452.  doi:

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A novel complex Zn₃(phen)₂(2,4-DAA)₆(2,4-DAA=2,4-dichlorophenoxy acetic acid phen=1,10 phenanthroline) was synthesized by means of hydrothermal method and characterized as crystallizing in the triclinic system with space group P1, a=1.1030(2) nm, b=1.2930(3) nm, c=1.5081(3) nm, α=100.436(3)°, β=110.227(3)°, γ=103.802(3)°, V=1.8760(7) nm³, D_c=1.661 g/cm³, Z=1, F(000)=944. Final GooF=1.033, R₁=0.0326, wR₂=0.0736. The crystal structure shows that the three coordinated zinc(Ⅱ) ions lie in the same line with the middle one as the symmetric center. The distance between the central zinc(Ⅱ) and the symmetric one is 0.3378 nm. There exist two coordination modes for the three zinc(Ⅱ) ions: (1) The symmetric zinc(Ⅱ) ions are coordinated with three oxygen atoms and two nitrogen atom from three 2,4-dichlorophenoxy acetic acid molecules and one 1,10 phenanthroline molecule, respectively, forming a distorted square-pyramid coordination geometry. (2) The middle zinc(Ⅱ) ions is coordinated with six oxygen atoms from six 2,4-dichlorophenoxy acetic acid molecules, respectively, forming a distorted octahedral coordination geometry. The luminescence and electrochemical properties of the complex are also studied.

Synthesis, Crystal Structure and Magnetic Property of a New Double Chainlike Heterobinuclear Supramolecular Architecture [Cu(oxbe)Ni(dpt)(H₂O)]ClO₄ ·0.5H₂O

LI Jian-Ding¹, ZHANG Wu¹, TAO Ruo-Jie¹*, WANG Qing-Lun², CHENG Yan-Xiang³

2008, 29(3):  453-456.  doi:

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A new heterobinuclear complex bridged by N-benzoato-N'-(2-aminoethyl)oxamido trianion(oxbe) and end-capped with dipropylenetriamine(dpt), [Cu(oxbe)Ni(dpt)(H₂O)]ClO₄·0.5H₂O, was synthesized and characterized by elemental analyses and IR spectra. The crystal structure was determined by single-crystal X-ray diffraction analyses. There are hydrogen bonds in the complex resulting in the formation of the double chainlike supramolecular architecture. The variable temperature magnetic susceptibility measured at 5—300 K indicates the presence of a medial antiferromagnetic interaction through the oxamido bridge in binuclear system Cu(S_Cu=1/2)-Ni(S_Ni=1) with magnetic parameters J=-62.3 cm^-1, g=2.11.

Preparation and Luminescence Characteristics of Sr₂SiO₄∶Dy³⁺ Phosphor

LI Pan-Lai*, YANG Zhi-Ping, WANG Zhi-Jun, GUO Qing-Lin

2008, 29(3):  457-460.  doi:

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The Sr₂SiO₄∶Dy³⁺ phosphor was synthesized by high temperature solid-state method. The emission spectrum of Sr₂SiO₄∶Dy³⁺ shows several bands at 486, 575 and 665 nm under the 365 nm excitation. The excitation spectrum for 575 nm emission has several excitation bands at 331, 361, 371, 397, 435, 461 and 478 nm. The effect of Dy³⁺ concentration on the emission spectrum intensity of Sr₂SiO₄∶Dy³⁺ was investigated, the result shows that the ratio(Y/B) of yellow emission(575 nm) to blue emission(486 nm) increases with increasing Dy³⁺ concentration, the 575 nm yellow emission intensity firstly increases with increasing Dy³⁺ concentration, then decreases. With the condition of immitting the charge compensation, the emission spectrum intensity of Sr₂SiO₄∶Dy³⁺ is enhanced, and the effect is most distinctly with immitting Li⁺.

Preparation and Luminescence Properties of Rod-like LaF₃∶Eu³⁺ Nanocrystals

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

2008, 29(3):  461-464.  doi:

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Rod-like LaF₃∶Eu³⁺nanocrystals were synthesized by a simple liquid method at room temperature, and the properties were characterized. XRD patterns showed that the hexagonal phase LaF₃ crystals with a better crystallinity were obtained at room temperature, the diffraction peaks intensities increased with the increase of annealing temperature and no impurity phase was observed. TEM images showed that the LaF₃∶Eu³⁺ nanocrystals are in rod shape with the diameter of 8 nm and length to 50 nm. Photoluminescence properties indicated that the strongest emission peak of the obtained rod-like LaF₃∶Eu³⁺ nanocrystal is near 589 nm, corresponding to the ⁵D₀-⁷F₁ transition of Eu³⁺, which suggests that Eu³⁺ is located at C₂ symmetry lattice of La³⁺ in LaF₃ host, in addition, the quenching molar fraction of Eu³⁺ is 5% and the lifetime increases with the increase of annealing temperature.

研究快报

Synthesis of Ordered Sub-mesostructured Silica via Ionic Liquid as Structure-Directing Agents

LI Shang-Yu², WANG Run-Wei², WAN Li-Feng², QU Xue-Jian², ZHANG Tao², ZHANG Zong-Tao¹*, QIU Shi-Lun^1,2

2008, 29(3):  465-467.  doi:

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An ordered hexagonal pore sub-mesostructured silica was synthesized via ionic liquid 1-hexadecane-3-methylimidazolium bromide(C₁₆MIB) as structure-directing agents in acidic media. By combining the results of transmision electron microscopy, X-ray diffraction and surface area measurements, an elementary structure and characterization of the samples was obtained. This material performs two-dimensional hexagonal framework structure being analogous to MCM-41 and SBA-3 silicas in long range order, but the position of reflection peaks of X-ray diffraction shifts to a wide angle compared with those of MCM-41 and SBA-3. The sub-mesostructured silica has high BET specific surface area of 1360 m²/g, as well as small pore size of 1.8 nm.

研究论文

Determination of Trace Level Nitroaromatic Explosives in Wastewater by Stir Bar Sorptive Extraction Coupled to Gas Chromatography

GUAN Wen-Na¹, XU Feng¹, MENG Zi-Hui², GUAN Ya-Feng¹*

2008, 29(3):  468-472.  doi:

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A novel poly(phthalazine ether sulfone ketone, PPESK) stir bar was prepared. The method for analyzing trace level nitroaromatic explosives in aqueous samples by stir bar sorptive extraction coupled to GC through thermal desorption was developed. The stir bar can be placed into thermal desorption unit after extraction at 250 ℃, so the sensitivity of the method can be enhanced because the analytes are completely transferred into GC column. The PPESK stir bar was proved to show one order of magnitude higher extraction capacity than the corresponding PPESK fiber and two orders of magnitude higher extraction efficiency than PDMS stir bar. The limits of detection(LODs) were in the range of 0.008—0.022 μg/L. The repeatability of the method(RSD) was from 6.9% to 15.9%, and the linear ranges were 0.06—10.0 μg/L with correlation coefficients of 0.9962—0.9998 except for TNT. By using the optimized extraction method, the wastewater samples produced in explosive production process were analyzed. The recoveries were from 88% to 100% for low concentration sample and from 61% to 88% for diluted high concentration sample. The RSDs of the repeatability of real sample application were lower than 11%.

Determination of Ceftiofur Residues in Milk by Receptor-based Microplate with Elisa Assay

LI Tie-Zhu¹, SUN Yong-Hai¹*, XI Wei-Dong^1,2

2008, 29(3):  473-476.  doi:

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The penicillin-binding protein PBP 2x from Streptococcus pneumoniae was utilized to develop a novel microplate assay for the determination of ceftiofur with intact β-lactam structure in milk. The assay was developed as screening test with the option for a quantitative assay for ceftiofur residues. Ceftiofur could be detected at levels corresponding to 1/5 EU maximum residue limit(MRL) in milk without lengthy and elaborate sample pre-treatment. Matrix calibration curves are presented, which show that quantitative analyses are possible.

Studies on Dispersibility of Different Functionalized Silica Nanoparticles

NIE Hai-Long, HE Xiao-Xiao, HUO Xi-Qin*, HAI Luo, WU Xu, GE Jia, TAN Wei-Hong

2008, 29(3):  477-481.  doi:

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Silica nanoparticles(SiNP), amino-terminated silica nanoparticles(NSiNP), carboxyl-terminated silica nanoparticles(CSiNP) and PEG-terminated nanoparticles(PSiNP) were prepared via the synchronous modification of functional group in water-in-oil microemulsion(hereinafter referred to being modified in oil) and the modification of functional group on the well-prepared SiNP(hereinafter referred to being modified in water) respectively. The dispersibility of different functionalized silica nanoparticles in water suspension was evaluated with sediment velocity and centrifugation velocity. And further analysis of the dispersion behavior was demonstrated through the TEM imaging and hydrodynamic size analyses. The results indicat that the following order of dispersion was observed: CSiNP≥PSiNP>SiNP>NSiNP, when the silica nanoparticles were modified with the same method. In addition, for CSiNP and PSiNP, the dispersibility of the two nanoparticles modified in oil was superior to that of modified in water. At the same time, the nonspecific adsorption of the different functionalized silica nanoparticles modified in oil with the Hela cells was also investigated. There was almost no nonspecification with Hela cells to CSiNP and PSiNP. However, the NSiNP were adsorbed to the Hela cells extensively. These results played important roles in the preparation and further modification of silica nanoparticles that would be well suited in biomedicine.

Studies on Competitive Reaction Between Bovine Serum Albumin and Ampicillin with Evans Blue as Fluorescent Probe by Fluorescence Spectroscopy

ZHAO Hu¹, PANG Yan-Ling², ZHANG Min¹, YUE Ning-Ning¹, LÜ Qing-Luan¹, ZHANG Miao¹, WANG Huai-You¹*

2008, 29(3):  482-487.  doi:

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The competitive reaction between ampicillin and bovine serum albumin(BSA) was studied with Evans blue(EB) as a fluorescence probe by the fluorescence spectroscopy. Fluorescence quenching occurred between the bovine serum albumin and Evans blue. The static fluorescence quenching process was confirmed on the basis of the Stern-Volmer plot. The binding constant(K_BSA-EB=1.122×10⁶ L/mol) and the number of binding sites(n=0.9935) were obtained. The enthalpy change, entropy change and free energy change were calculated, and the types of interaction force between EB and BSA were investigated. The relative fluorescence intensity of BSA was recovered gradually with increasing the concentration of ampicillin. The results indicate that there was a competitive interaction between ampicillin and EB for BSA, and the interaction mechanism was studied, the binding constant of EB with ampicillin, K_EB-A=7.131×10⁵ L/mol, was obtained.

Studies on Binding Equilibrium Between As(Ⅲ)/As(Ⅴ) and BSA via Dialysis and High Performance Liquid Chromatography-Hydride Generation On-Line Coupled with Atomic Fluorescence Spectrometry

JIANG Hong*, DING Jing-Hua, ZHANG Ying-Hua, GONG Hui-Zhi, GAO Shuang, SUN Gui-Fan

2008, 29(3):  488-492.  doi:

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The binding equilibrium of As(Ⅲ)/As(Ⅴ) to bovine serum albumin(BSA) was studied by Dialysis and High Performance Liquid Chromatography-hydride generation on-line coupled with atomic fluorescence spectrometry(D-HPLC-HG-AFS) at physiological(pH=7.4). The binding plots analysis indicates that the binding model is Scatchard when the concentrations of As(Ⅲ) ions are lower[c_As(Ⅲ)∶c_BSA≤1∶1], there is 1.4 strong binding site of As(Ⅲ) ions in BSA, the stability constants is 1.7×10⁶ at physiological(pH=7.4). The binding model is Plasvento when the concentrations of As(Ⅲ) ions are higher(c_As(Ⅲ)∶c_BSA≥2∶1], and As(Ⅴ) ions has litter effect on BSA. The method based on HPLC-HG-AFS for arsenic speciation analysis was developed. The factors of the method including HPLC mobile phase, concentrations of HCl, flow rate of HCl, concentration and flow rate of KBH₄ were investigated in this paper. Under the optimum conditions, the detection limits for As(Ⅲ) and As(Ⅴ) were 2.89, 6.38 ng/L, respectively.

Preparation of a New Thiophene Heterocyclic β-Cyclodextrin Derivative as GC Stationary Phase and Gas Chromatographic Isomer Separation Performance

ZHOU Mei-Yang, LING Yun, SHEN Gang-Yi, YANG Xin-Ling*

2008, 29(3):  493-497.  doi:

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A new thiophene heterocyclic β-cyclodextrin derivative, 2,6-di-O-allyl-3-O-[2-(prop-1-en-2-yl)thiophene]-β-CD(GCPS1), was prepared and used as a GC stationary phase. It’s separability for some benzenic isomers and pyrethroic derivatives enantiomers was studied. The result shows that the separation for some benzenic isomers is better than that in the literature. And in meanwhile, four chiral pyrethroic derivatives can be separated well on the column where GCPS1 was used as the gas chromatography stationary phase.

Preparation of Protein Molecularly Imprinted Composite Membrane by Sol-gel Coating Method and Its Permeation Mechanism

ZHANG Mo¹, HE Xi-Wen¹, QIN Lei¹, LI Wen-You¹*, CHEN Lang-Xing¹, ZHANG Yu-Kui^1,2*

2008, 29(3):  498-504.  doi:

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Composite MIMs were prepared by poly[acrylamide] sol-gel coated Nylon microfiltration membranes with BHb, BSA and LYZ as the template molecules, respectively. The surface and cross-section morphology of the MIMs were studied by scanning electron microscopy. It is found that both the outer and inner surface of the Nylon membrane were coated by the sol-gel. The permeation experiments were carried out with both the single template and the double components containing the template and its competitive analogue. The results of permeation experiments show that the permeation of the template is attributed to both the size effect and its complementary functional groups and shape with the imprinted sites. The specific imprinted sites could selectively rebind the template, resulting in the slower permeation of the template. And the size effect means that the smaller the size is, the faster the template transports.

Matrix Molecularly Imprinted Polymer for Enriching Lysozyme in Protein Samples

LIU Qiu-Ye¹, GAI Qing-Qing¹, HE Xi-Wen¹*, LI Wen-You¹, CHEN Lang-Xing¹, ZHANG Yu-Kui^1,2*

2008, 29(3):  505-509.  doi:

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The effects of the molar ratio of functional monomer to template protein, the pH and the ionic strength of the medium on the interaction between the functional monomers and template protein were primarily investigated from the molecular level by UV spectrophotometry. Then lysozyme(Lyz)-imprinted polyacrylamide gel was prepared to recognize effectively Lyz in protein samples. With acrylamide and N,N’-methylenediacrylamide as the polymeric matrix and silica as the pore-forming reagent, after template and silica were removed, the surface of gel polymer had a large quantity of well-distributed macropores, which were suited to let the proteins pass in and out. The recognition and selectivity of the imprinted polymers were studied with equilibrium adsorption. Selective adsorption experiments of the imprinted gel show that imprinted gel exhibited good recognition capability for Lyz compared with bovine serum albumin or ovalbum as the completive substance.

Resonance Rayleigh Scattering Spectra of the Interaction of Pd(Ⅱ)-Methotrexate Chelate with Methylene Blue and Their Analytical Application

XI Cun-Xian, LIU Zhong-Fang, LIU Shao-Pu*, HU Xiao-Li, ZHENG Tian-Long

2008, 29(3):  510-514.  doi:

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In Britton-Robinson buffer of pH 4.1—7.0, methotrexate reacts with palladium(Ⅱ) to form 1∶1 anionic chelates. Which react further with methylene blue(MB) to form the ion-association complexes. In this case, the resonance Rayleigh scattering(RRS) intensities are enhanced greatly and new RRS spectra appear. The maximum RRS wavelengths locate at 342 nm. Under given conditions the intensities of RRS are proportional to the concentration of MTX. The linear range is 0.008—2.0 μg/mL for the system, and the methods have high sensitivities and the detection limits of MTX is 2 ng/mL. The optimum conditions of the reaction, influence factors and the effect of coexisting substances were investigated. A high sensitive, simple and quick method is developed for the determination of MTX. The method can be applied satisfactorily to determination of MTX in serum and urine samples. In addition, the structure of the ternary ion-association complex and their reaction mechanism were discussed.

Proteome Study of Differential Protein Expression in Acute Infracted Rat Heart after Verapamil Treatment

LI Ying, WANG Yi*, QU Hai-Bin, CHENG Yi-Yu

2008, 29(3):  515-518.  doi:

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To explore the protein-level action mechanism of verapamil in acute myocardial infracted rats, the myocardial proteome was analyzed by two-dimensional electrophoresis(2-DE). In comparison with the sham-operated group and the infracted group, the result shows that eight proteins expressions in verapamil treated group were up-regulated, and seven proteins expression in this group were down-regulated significantly. By using MALDI-TOF-MS, 15 proteins with significant changes were identified by database searching. These proteins can be divided into four groups via their biological function: (1) energy metabolism and mitochondrial function related proteins; (2) oxidative stress-induced proteins; (3) cytoskeletal proteins; (4) other proteins. The findings show that the myocardial protective effects of verapamil in myocardial damage process were related to the recovery of energy supply as well as anti-oxidative stress property.

Synthesis and Fluorescent Properties of Triazine-based Dendrimers Functionalized with 1,4,5,8-Naphthalimide Group

SUN Jin-Yu*, WANG Xi-Xi

2008, 29(3):  519-522.  doi:

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Without employing protection or deprotection steps, a novel series of fluorescent triazine dendri-mers of three generations containing of a single, focally located 1,4,5,8-naphthalimide-based core and 8, 16 ethyl peripheral groups were synthesized with convergent approaches, and fully characterized via IR, ¹H NMR, ¹³C NMR and elemental analyses. Using this method, a mild reaction condition was allowed, and an excellent yield was obtained. Their fluorescent properties in dichlomethane were studied. The results indicate that the triazine dendrimers have stronger fluorescence, and their intensity increased according to generation number increase.

Design and Synthesis of Amide KARI Inhibitors and Their Biological Activities

WANG Bao-Lei, LI Zheng-Ming*, LI Yong-Hong, WANG Su-Hua

2008, 29(3):  523-527.  doi:

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Ketol-acid reductoisomerase(KARI) is a promising target for the design of herbicides, however, there are only few literatures about the molecular design of KARI inhibitors. In this paper, on the basis of the reported 0.165 nm high resolution crystal structure of spinach KARI complex, 279 molecules with a low binding energy toward KARI were obtained from MDL/ACD 3D database searching by program DOCK 4.0. According to the structural information of 279 molecules provided, some amide compounds were synthesized. The bioassay results show that most of these amides had an inhibitory activity to rice KARI at a test concentration of 200 μg/mL, Among the eight amides synthesized, compounds 1 and 6 showed 57.4% and 48.1% inhibitory activity to KARI. The herbicidal activities of these amides were further investigated on di-cotyledonous rape(Brassica campestris) and mono-cotyledonous barnyardgrass(Echinochloa crusgalli). Compounds 1 and 6 were more favorable than others and showed 52.0% and 72.6% inhibitory activity on rape root at 100 μg/mL concentration, which was correlated with their in vitro activity to KARI. These amides KARI inhibitors designed can be further optimized for finding more potent KARI inhibitors and herbicide candidates as well.

Construction of Phage-displayed Library Based on the Lipocalin Scaffold and Screening Anticalins with Specificity for Carbofuran

WU Jie^1,2, YANG Jing-Yi¹, ZHANG Hong-Bin², PAN Ke¹,WANG Hong¹, LEI Hong-Tao¹, ZHENG Lin¹, XIAO Zhi-Li¹, SUN Yuan-Ming¹*

2008, 29(3):  528-532.  doi:

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Carbofuran, which is used as toxic carbonate pesticide of crops, is highly toxic and small molecule. To detect the remainder of carbofuran efficiently is important to our healthy. The lipocalins, a family of diverse proteins that normally serve for the storage or transport of mostly hydrophobin and/or chemically sensitive organic compounds, can be reshaped by combinatorial protein design such that it recognizes small molecules. Sixteen residues at the center of binding site of the bilin-binding protein(BBP) from Pieris brassicae were subjected to random mutagenesis by overlapping PCR with 12 primers. Phagemid expression vector of pCANTAB5E was used to construct the lipocalin library. The library repotire is4.0×10⁹. BSA and OVA conjugated carbofuran respectively as the targeted protein, the library was screened with column and plate as supporter. After 3 rounds of panning, 10 phage clones were random selected with competitive elution. Dot-blotting showed that phage displayed anticalin, named as K7, bound carbofuran specifically among them. K7 can be used as potential anticalin to detect carbofuran of crops.

Syntheses and Crystal Structure of 1,5-Benzothiazepine Derivatives Containing Pyrazole

XING Ye¹, XIE Zheng-Feng¹*, LIU Fang-Ming²*

2008, 29(3):  533-536.  doi:

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Ten chalcones were synthesized by Aldol condensation reaction of acetophenone or para-substituted acetophenones with 1-phenyl-3-methyl-5-aryloxyl- pyrazol-4-aldehyde under the strong alkali condition, then chalcones reacted with 2-aminobenzenethiol in glacial acetic acid under refluxing to give a series of 1,5-benzothiazepine which have potentially useful pharmacological properties. The compounds were confirmed by means of elemental analysis, IR spectrum, ¹H NMR and X-ray single-crystal diffraction analysis. The crystal of compound 6c belongs to a monoclinic system, space group P2(1)/n with cell parameters a=1.1793(2) nm, b=1.1907(2) nm, c=1.8726(4) nm, α=90°, β=104.71(3)°, γ=90°, M=522.04, V=2.5432(9) nm³, D_c=1.363 Mg/m³, Z=4, F(000)=1088.

Chemoselective Reduction Model of Aliphatic Esters with Sodium Borohydride

LÜ Xiao-Jie^1,2, JIANG Ju-Xing^1,2, REN Jie¹, ZHU Hua-Jie¹*

2008, 29(3):  537-541.  doi:

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Sodium borohydride has been widely used in different organic reductions due to its moderate chemical activity. The reductions of ester with sodium borohydride could produce various alcohols as intermediates for further reactions. The esters with different alkyl substituents are used as the models in sodium borohydride reductions, and on-set temperatures, half-life periods and transition state(TS) energies were obtained experimentally. Some of the TS energetics were computed using B3LYP/6-31++G(d,p)//HF/6-31G(d,p) method. The differences of on-set temperatures among these esters were substantial and some observed selectivities were obtained when the aliphatic substituents changed from Me, Et, n-Pr to n-Bu. Odd-even carbon effect, which was first mentioned in our previous report in enantioselective additions of diethylzinc to benzaldehyde, was observed again in the reductions. Traditionally, organic theory uses the size of the substitutents to explain the reaction TS energy order. However, the traditional theory can not be used to explain the observed odd-even carbon effect. The reason for this effect happened in different reactions is still unknown. Furthermore, the effect of solvent in the reductions was investigated primarily.

Synthesis and Biological Activities of Hemoglobin Fragments

LI Xiao-Hui¹*, YUAN Heng-Li¹, HU Jian-En², XIU Zhi-Long¹

2008, 29(3):  542-545.  doi:

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The peptides can be obtained by enzymatic proteolysis of food proteins and may act as potential physiological regulators of metabolism during the intestinal digestion of diet. To investigate bioactive peptides within food proteins, six peptides derived from α-chain of hemoglobin were synthesized via peptide solid-phase method. The peptides were purified on Sephadex LH-20 gel chromatography column and detected by RP-HPLC and MS respectively. In vitro bioactivity of Leu-Gly-Phe-Pro-Thr-Thr-Lys-Thr-Tyr-Phe-Pro-His-Phe showed similar activity(IC₅₀=4.76 μmol/L) in inhibition of angiotensin I-converting enzyme(ACE) compared with that obtained from globin hydro-lysis(IC₅₀=4.92 μmol/L). These results confirm that the peptide inhibitors of ACE, which contain a hydrophobic amino acid at C-terminal with branched side chain(e.g. Leu, Phe, Pro), are more active. No α-glucosidase inhibitory activity was detected. The results indicate that these peptides have a potential antihypertensive effect and possible application in remedy of hypertension

NMR Study of Influences of D51N Mutation on Backbone Conformation of Hyperthermophilic Archaeal [P62A]Ssh10b

LUO Quan^1,2, FANG Xian-Yang¹, DENG Zhi-Wei², WANG Jin-Feng¹*

2008, 29(3):  546-550.  doi:

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The P62A mutant hyperthermophilic archaeal protein Ssh10b, [P62A]Ssh10b, is highly thermostable. The structure determination shows that a salt-bridge K48—D51 is formed in helix α2, and mutation of D51 can influence the thermostability of protein. In order to understand the effect of mutation on the stability of protein, we constructed the D51N-mutant [P62A]Ssh10b plasmid, and obtained the ¹⁵N and ¹³C double-labeled [D51N/P62A]Ssh10b protein with a high purity. The experimental data of triple-resonance NMR experiments provided nearly complete backbone resonance assignments. Comparing the main chain ¹H^N and ¹⁵N chemical shifts for [P62A]Ssh10b with its mutant variant and analyzing the chemical shift differences on the basis of [P62A] Ssh10b structure, it was found that D51N mutation influenced the backbone conformation of helix α2. The further effect was observed in the structural region consisting of Loop L_β2α2, the N-terminal of strand β4, and the C-terminal of loop L_β3β4, and in the region around loop L_β3β4 as well. This revealed that D51N mutation disrupted the salt bridge of K48—D51 on helix α2 and influenced not only the backbone conformation of helix α2 but also the local conformations of other structural regions in the protein. Therefore, the high thermostability of [P62A]Ssh10b may be correlated closely to its tertiary conformation.

研究快报

Structure Elucidation of Two Major Saponins from Lonicera fulvotomentosa Hsu et S.C.Cheng

TANG Dan, LI Hui-Jun, LI Ping*, ZHAO Shi-Yan, BI Zhi-Ming

2008, 29(3):  551-553.  doi:

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A new triterpenoid saponin was isolated from Lonicera fulvotomentosa. The structure of the new tri-terpenoid saponin, named Fulvotomentoside B, was elucidated as 3-O-β-D-xylopyranosyl(1→3)-α-L-rhamnopyranosyl(1→2)-α-L-arabinopyranosyl hederagenin-28-O-β-D-xylopyranosyl(1→6)-β-D-glucopyranosyl ester on the basis of spectroscopic analysis as well as chemical methods. In addition, the structure of Fulvotomentoside A, the previously reported major saponin, was revised, and it should be 3-O-β-D-xylopyranosyl(1→3)-α-L-rhamnopyranosyl(1→2)-α-L-arabinopyranosyl hederagenin-28-O-β-D-glucopyranosy(1→6)-β-D-glucopyranosyl ester(Decaisoside E) on the basis of careful analyses of new spectroscopical data.

研究论文

Studies on the Photocatalytically Degradable Polyethylene Films

CHEN Yi^1,2*, YUAN Shuai¹, SHI Li-Yi^1,3, ZHU Huan-Yang^2,3, ZHANG Jian-Ping³

2008, 29(3):  554-558.  doi:

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The photocatalytically degradable composite films were synthesized by using low density polyethylene(LDPE) and acid blue BGA sensitized nano-TiO₂. SEM, Digital microscope of VHX-100, FTIR, High temperature gelatin permeation chromatography(HTGPC) and other analytic techniques were used to characterize the films before and after irradiation under UV light or sunlight. The results reveal that the degradation efficiency of sensitized TiO₂/PE composite films was increased greatly. After irradiation under UV light for 5 days, the dye sensitized TiO₂/PE composite film lost 17.6%(mass fraction) weight, and the number-average molecular weight(M_n) decreased from 21800 to 5900. After irradiation under sunlight for 48 days, the dye sensitized TiO₂/PE composite film lost 12.5%(mass fraction) weight, and the M_n decreased to 8100. After irradiation, the tensile strength and elongation at break of the films decreased obviously, and the content of carbonyl increased greatly.

Investigation on Microbial Fuel Cell with Permanganate as Cathode

ZHAN Ya-Li*, WANG Qin, YAN Guang-Xu, GUO Shao-Hui

2008, 29(3):  559-563.  doi:

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In the present paper a microbial fuel cell(MFC) was constructed with acetate solution as the fuel in anode cell and potassium permanganate as oxidized agent in cathode cell. The influences of the concentration, flowing status and pH value of cathode solution, and outer resistance on the MFC were investigated, outer voltage and electrode potentials were monitored and the influence factors on cathode and cell were analyzed. The results show that: (1) MnO₂ deposition on the surface is the main factor resulting in cathode polarization, and the flowing of the solution can remarkably reduce this polarization. Furthermore, the buffered solution can reduce the polarization resulting from H+ concentration difference; (2) it is deduced from the polarization curve that the key factor influencing the performance of MFC is microbial number and metabolic rate and the electron transferring rate from microbial to electrode; (3) the power density arrives at the biggest, 824 mW/m², when outer resistance is 300 Ω, which is accordance to the inner resistance, (284±18) Ω, deduced from I-V curve; (4) the influences of pH and permanganate concentration on cathode potential is in agreement to Nernst equation.

Research of AC Impedance of Dynamic Behavior of Direct Methanol Fuel Cell

LI Jia-Chun^1,2, XIE Xiao-Feng²*, GUO Jian-Wei², QI Liang², ZHOU Tao¹*

2008, 29(3):  564-568.  doi:

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Electrochemical Impedance Spectrum (EIS) was employed to investigate the dynamic behavior and interior mechanism of direct methanol fuel cell(DMFC) in working states. The spectrums were simulated through the equivalent circuit of L₁R₁[QR₂(L₂R₃)], and the results show that the high inductance L₁ was only related to the EIS measurement process. Meanwhile, the system resistance R₁ and charge transfer resistance R₂ was shown to decrease gradually but was affected by mass transfer at high discharging current. Both the low inductance L₂ and low frequency resistance R₃ in circuit reflected the adsorption/desorption balance of intermediate species originating form methanol oxidation reaction, which decreased with the discharge current increasing. The constant phase elements(CPE) Q in this circuit was mainly influenced by the driving forces of both reactions and mass transfer, and indicated that there existed a transition process from ideal capacitance to the charge transfer with the discharging current increasing.

Studies on the Enthalpy of Solution of Ionic Liquid [C2mim][FeCl4] Based on Transition Metal

ZHANG Zi-Fu1, WANG Heng1, FANG Da-Wei1,2, YANG Jia-Zhen1*

2008, 29(3):  569-572.  doi:

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A brown and transparent ionic liquid,[C₂mim][FeCl₄], was prepared by mixing anhydrous FeCl₃ with 1-methyl-3-ethylimidazolium chloride([C₂mim][Cl]), with molar ratio 1∶1 under stirring in a glove box filled with dry argon. The molar enthalpies of solution, Δ_sH_m, of [C₂mim][FeCl₄] in water with various molalities were determined by a solution-reaction isoperibol calorimeter at 298.15 K. In terms of Pitzer electrolyte solution theory, the standard molar solution enthalpy of [C₂mim][FeCl₄], Δ_sH⁰_m, and the sum of Pitzer parameters: (β^(0)L_Fe,Cl+β^(0)L_[C2min],Cl+Φ^L_Fe,[C2min]) and (β^(1)L_Fe,Cl+β^(1)L_[C2min],Cl) were obtained, respectively. Using the values of the solution enthalpies and crystal energy of the ionic liquid, the dissociation enthalpy of [FeCl₄]^- anion, ΔH_dis≈5659 kJ/mol, for the reaction: [FeCl₄]^-(g)→Fe³⁺(g)+4Cl^-(g), was estimated. It is shown that the enthalpy of solution of the[C₂mim][FeCl₄] is small because the large hydration enthalpies of Fe³⁺, 4Cl^- and [C₂mim]^- was compensated by the large dissociation enthalpy of [FeCl₄]^- anion, Δ_dH_m, in dissolution process of the IL.

Amorphous Si/Al/Si Film Anode Material for Lithium-ion Battery

SONG Ying-Jie¹, ZHANG Hong-Fang¹, FU Ping-Ping¹, YANG Hua-Bin¹*, ZHOU Zuo-Xiang¹, WU Meng-Tao², HUANG Lai-He²

2008, 29(3):  573-577.  doi:

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A sandwich-type Si/Al/Si film was prepared on copper substrate by magnetron sputtering. High-resolution transmission electron microscopy(HRTEM) and selected area electron diffraction(SAED) results indicat that the sputtered film had an amorphous structure. Cross-sectional scanning electron microscope(SEM) images and energy dispersive X-ray spectrometry(EDS) spectra show that the thickness of the film was about 4.0 μm, and its expansion ratio was up to 225% after 100 cycles. In the potential range 1.5—0.005 V(vs. Li⁺/Li) at the current density of 0.1 mA/cm², this film anode exhibited an initial capacity around 0.88 mA·h/cm², 0.71 mA·h/cm² after 5 cycles, and still retained over than 0.61 mA·h/cm² after 100 cycles. The addition of Al to Si effectively suppressed the volume expansion, which led to a prolonged cycle life. Electrochemical impedance spectroscope(EIS) results indicat that the polarization resistance first decreased to 36.2 Ω·cm²(50th cycle) from 46.9 Ω·cm²(1st cycle) and later increased to 47.3 Ω·cm²(100th cycle) during cycling. The introduction of Al to Si improved the conductivity of the Si film and reduced the polarization resistance, which suppressed the voltage hysteresis effect.

Electro-generation of Thioglycolic Acid Using mCMC-PEG-CS Bipolar Membrane as Separator in Electrolysis Cell

CHEN Ni-Na^1,2, CHEN Ri-Yao¹, ZHENG Xi¹, CHEN Xiao¹, CHEN Zhen¹*

2008, 29(3):  578-584.  doi:

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mCMC-PEG-CS bipolar membrane(BM) was prepared by cation and anion exchange membrane. Cation exchange membrane was prepared with polyethylene glycol(PEG)-sodium carboxymethyl cellubse(CMC) blends which were modified by Fe³⁺, and anion exchange membrane was prepared by PEG-chitosan(CS) blends which were modified by glutaraldehyde(GA), rspectively. mCMC-PEG-CS bipolar membrane was used as a separator in the electrolysis cell to produce thioglycolic acid(TGA). Thioglycolic acid(TGA) was prepared by electro-reduction of dithioglycollic acid(DTDGA) with the mixture of TGA and DTDGA as the raw materials. The influences such as acid concentration, temperature and electrolysis current densities on the electro-generation and the current efficiency of TGA were studied. The experiment results show that TGA was prepared effectively by electroreduction of dithioglycollic acid(DTDGA) with the mixture of TGA(2.79%) and DTDGA in the cathodic room. The current efficiency was up to 74.69% at 35 ℃ in a cylinder electrolysis cell at 10 mA/cm². To compare with the traditional of metal reduction method, the electro-reduction technology saves the zinc powder and eliminates the pollution to environment.

Studies on the Heme Prosthetic Group’s Geometry by ABEEM/MM Method

CUI Bao-Qiu^1,2, GUAN Qing-Mei¹, GONG Li-Dong¹, ZHAO Dong-Xia¹, YANG Zhong-Zhi¹*

2008, 29(3):  585-590.  doi:

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Applying the developed parameters, the heme prosthetic group was simulated by the ABEEM/MM method. The results show that these simulations can reproduce better X-ray structures than CHARMM method. The distorted ruffing conformational energies obtained from the ABEEM/MM method agree well with those by B3LYP/6-31G* method. The linear correlation coefficient R is over 0.98. The investigations show that the twist-angles have important effects on the ruffing conformational energies. The accurate charge for Cytochrome c₅₅₂ from ABEEM/MM method can be used to investigate better the polarization effects than those from CHARMM method.

Property Analysis of Inhibitors-binding Site of Bcl-2 Protein

ZHENG Can-Hui, ZHOU You-Jun*, ZHU Ju, CHEN Jun, LI Yao-Wu, SHENG Chun-Quan, SONG Yun-Long, LÜ Jia-Guo, JIANG Jun-Hang, LIU Na

2008, 29(3):  591-595.  doi:

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Bcl-2 protein is a new target of anticancer drugs with a bright prospect now. The multiple copy simultaneous search(MCSS) methodology was used to analyze the inhibitors-binding site of Bcl-2. The results show that the inhibitors-binding site can be divided into five subsites(P1, L1, P2, P3, P4), the bottom of which is hydrophobic. And several important residues which can form interactions other than hydrophobic interactions distribute on the side and edge of the inhibitors-binding site. Energetically favorable positions and orientations of various functional groups determined by MCSS computing are consistent with these of important groups in high potent inhibitors, which can reversely guide the structure modification and novel design of inhibitors effectively.

Dynamic Study of Reactions Between Ca Atoms with Ground State and CH₂Cl₂ by Quasi-classical Trajectory Method

ZHANG Zhi-Hong^1,2, CHEN Mao-Du¹*, CONG Shu-Lin¹

2008, 29(3):  596-599.  doi:

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The dynamics of the reaction Ca+CH₂Cl₂ was studied with quasi-classical trajectory calculation based on a constructed extended-LEPS potential energy surface at the first. The calculated results show that the product CaCl vibrational population peaks are located at ν=0 with collision energy E_col=9.632 kJ/mol. This product state distribution agrees well with experiment data. The cross-section decreases rapidly in the beginning and slowly in the end with the collision energy increasing, and 〈P₂(J’·K)〉 values deviated slightly from -0.5 and collision energies in the range from 6.276 to 86.684 kJ/mol were obtained.

Theoretical Investigation for the Electronic Structure and Electronic Spectrum of F-substituted Pt(Ⅱ) Complexes

LIU Xiao-Dong^1,2, FENG Ji-Kang^1,2*, REN Ai-Min¹, YANG Bing³, XU Hai³

2008, 29(3):  600-604.  doi:

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The ground state, excited-state and electronic spectra in the Pt(Ⅱ)complexes, an important phosphorescent material, are studied with density functional theory(DFT)B3LYP/LanL2DZ. The low-energy absorptions are all assigned as the mixture of MLCT [d(Pt)→π*(ppy)] and LLCT [π(phenyl)→π*(ppy) or π(2,4-pentanedionato-O,O)→π*(ppy)]. It is found that F-substitutions in(2-phenylpyridinato-N,C2’) platinum(Ⅱ)(2,4-pentanedionato-O,O) result in the decrease of both HOMO and LUMO energies. Significantly, the HOMO-LUMO bandgap of F-substituent at the 2th or 4th position of phenyl in Pt complex is found to be increased, as a result its absorption and emission spectra are greatly blue-shifted. It provides an approach to control the emission color of Pt complexes by changing the substituents and their positions.

Molecular Dynamics Simulation of Adsorbed Chain’s Conformations of Copoly(vinylidene fluoride-chlorotrifluoroethylene) at 1,3,5-Triamino-2,4,6-trinitrobenzene Surface

NIE Fu-De^1,2, LIU Jian³, LI Jin-Shan², ZHAO Xiao-Ping³, LI Yue-Sheng¹, FAN Zhong-Yong¹*

2008, 29(3):  605-610.  doi:

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The surface absorption energy and the absorbed chains’ conformation were investigated by molecular dynamics(MD) simulations using compass force field and NVT ensemble model, in the case of poly(vinylidene fluoride)(PVDF), polychlorotrifluoroethylene(PCTFE) and their copolymers being absorbed on the crystal surface of 1,3,5-triamino-2,4,6-trinitrobenzene(TATB). The results show that the absorption exothermic effect appeared as the distance between polymer chains and the TATB crystal surface shorten to less than 0.8 nm. The absorption effect of PVDF was strong on the TATB crystal surface and it was reverse of PCTFE. MD simulations of alternative copolymers and random copolymers, with VDF and CTFE monomer ratio varying with 1∶1, 1∶2, 1∶3 and 1∶4 respectively, were carried out. The results indicte that the composition and serial structure of polymer chain influenced significantly the chain’s spatial conformations and its absorption behavior on TATB crystal surface. Especially, the alternative copolymer with the monomer ratio of 1∶2 showed the best absorption effect, attaching TATB crystal surface with train-conformations. As CTFE fraction increased, the stiffness of the copolymer was also increased, while the absorption ability and absorption energy decreased gradually with more tail and loop conformations formed.

Theoretical Study on the Low-lying Electronic States and Ionization Spectra of Fluorine Nitrate

WEI Zi-Zhang¹, LI Bu-Tong¹, PAN Qing-Jiang², ZHANG Hong-Xing¹*

2008, 29(3):  611-614.  doi:

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Using the complete active space self-consistent field(CASSCF) method with the atomic natural orbital(ANO) basis set, we studied the ground state and low-lying excited states of fluorine nitrate and its cation. The stable geometry of ground state was the planar structure with the C_s symmetry, but the stable structures of excited states were changed to the nonplanar structure. However, the similar change of the cation geometry was not observed. Furthermore, the vertical ionization potential of the fluorine nitrate molecular was studied on the basis of the optimized geometry of the ground state. Taking the dynamic correlation effects into account, we used the second-order perturbation(CASPT2) method to obtain more reliable energies. The assignment of the first two bands is in an excellent agreement with the experimental data and the theoretical results, but in the higher energy region, the different assignments were completed bass of the CASPT2 results.

Theoretical Mutation Design of Active Agent of Eryhropoietin and Its Receptor

QI Yan-Feng¹, GAO Xue-Feng¹*, HUANG Xu-Ri²

2008, 29(3):  615-617.  doi:

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Methods of molecular dynamics simulations were used to investigate the structure, dynamics and thermodynamics of the known complex between erythropoietin mimetic peptides(EMPs) and erythropoietin receptor(EpoR). On the basis of these results, we designed new kinds of EMPs that has proposed significance in binding toreceptor. We used amino acid residues which have more electricity ability to replace the hydrophobic ones. According to our calculation results, the mutant type peptide has more binding ability to the EpoR. Our results illustrate a principle for fast identifying receptor-specific site important for receptor interralization, and for enhancing sensitivity to horm on and other agonist.

Preparation of Tunable Colloidal Crystals Based on Temperature-sensitive Hydrogel

ZHENG Da, SUN Li-Guo, XIE Zhuo-Ying, XIONG Gui-Rong, XU Hua, GU Zhong-Ze*

2008, 29(3):  618-622.  doi:

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Wet type colloidal crystals were fabricated on the temperature-sensitive hydrogel PNIPAAm by dip-coating method. Optical properties of the colloidal crystals were controlled by taking advantage of the water-releasing effect of PNIPAAm. It is found that monodisperse spheres could form ordered three-dimensional structure on the surface of PNIPAAm by lifting hydrogel-coated substrate from latex suspension. The colloidal crystal on hydrogel exhibited a sharp reflection peak originating from the diffraction of light. By raising the temperature over 34 ℃, phase transition occurred for PNIPAAm. Accompanying with the phase transition, water in PNIPAAm was released to the colloidal crystal, which diluted the concentration of the spheres and increased the interparticle distance. As a result, the reflection peak shifted to the long wavelength side. Such a change can be recovered by decreasing the temperature.

Preparation of Porous Alumina from Ion-exchange Resins and Separation of Terpene Lactones in the Extract of Ginkgo biloba Leaves

REN Ping, WANG Mu-Li, WU Chun-Mi, WANG Chun-Hong*, WANG Wei*

2008, 29(3):  623-627.  doi:

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A method for preparing porous alumina beads using a cation exchange resin with sulfonic acid groups as templates was reported. And the beads were characterized by using XRD, SEM and BET method . The adsorption selectivity of the beads towards flavonol glycosides and terpene lactones was discussed, and adsorption mechanism was investigated by FTIR. The beads were used to separate terpene lactones from the extract of Ginkgo biloba leaves. And the purity of terpene lactones in the product was 58.5%, furthermore, there were no flavonol glycosides in it.

Preparation of Silk Fibroin Nanoparticles and Their Application to Immobilization of L-Asparaginase

ZHANG Yu-Qing*, XIANG Ru-Li, YAN Hai-Bo, CHEN Xiao-Xiao

2008, 29(3):  628-633.  doi:

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After the degummed fiber of silk fibroin derived from Bombyx mori cocoon was dissolved in CaCl₂ ternary solvent system or highly concentrated LiBr solution, three kinds of silk fibroin in liquid could be obtained by means of dialysis. SDS-PAGE analysis results show that three kinds of silk fibroin are of different molecular ranges. The silk fibroin nanoparticles were prepared rapidly from the liquid silk by using water-miscible organic solvents such as acetone. These nanoparticles are insoluble in water but well dispersed and stable in aqueous solution and are globular particles with a size range of 50—120 nm in diameter by means of SEM. L-Asparaginase as a model enzyme was bioconjugated with these nanoparticles by cross-linking agent glutaraldehyde. Activity analysis results indicate that silk fibroin nanoparticles derived from the fibroin by less breakage of peptide chain are more suitable for the bioconjugation of enzymes. The results show that the recovery of the immobilized L-asparaginase was about 44%. Its theromal stability increased evidently and the optimal scale of pH was much wider(pH 6.0—8.0) than that of native L-asparaginase. And the optimal reaction temperature of the modified enzyme was increased about 10 ℃. These preliminary results above indicat that the silk protein nanoparticles are also a good support as silk fibroin membrane. Therefore, the silk fibroin nanoparticles as a new drug release system are of potential values for study and development.

Preparation and Spectroscopic Properties of Line-Type Poly(glyceryl methacrylate) Bonding Manganoporphyrin on Side Chain

ZHANG Yan, WANG Rui-Xin, GAO Bao-Jiao*, GUO Hao-Peng

2008, 29(3):  634-639.  doi:

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The special chemical structures and properties of porphyrins make them have wide applications in many fields, such as biomimetic catalysis, electrocatalysis, chemical and biological sensors, solar energy conversion, and so on. If polymeric materials are functionalized with porphyrins, a new class of functional polymeric materials will be obtained, and it will have potential applications in advanced science and technology fields. In this paper, a valuable and significant exploration in the immobilization of porphyrins onto polymeric materials or the functionalization of polymers with porphyrins was studied based on poly(glyceryl methacrylate)(PGMA). Meso-tetra(4-hydroxylphenyl) porphyrin(THPP) was synthesized by adopting Adler’s method. The bonding reaction between PGMA and THPP was carried out in a homogeneous system, (hydroxylphenyl) porphyrin was bonded on the side chains of PGMA, and porphyrin-bonding PGMA was obtained(denoted as HPP-PGMA). Further, the coordination reaction between HPP-PGMA and MnCl₂ was performed and manganese porphyrin-bonding PGMA was gained(denoted as MnP-PGMA). The structure of HPP-PGMA was characterized with ¹H NMR spectrum. The electronic absorption and fluorescence emission spectra of HPP-PGMA and MnP-PGMA were determined and their photophysical behavior was examined. The experimental results show that(hydroxylphenyl) porphyrin and its manganese complex can be favorably bonded on the side chains of PGMA via the ring-openibg reaction between epoxy bonds on the side chains of PGMA and the hydroxyl groups of THPP, and line-type HPP-PGMA and MnP-PGMA were prepared successfully. HPP-PGMA possesses the characteristic electronic absorption spectrum and fluorescence emission of porphyrins, and MnP-PGMA have the characteristic electron absorption spectrum and fluorescence emission of original manganese porphyrins.

Preparation, Characterization and Properties of Polyaniline-barium Ferrite Nanocomposite

LI Yuan-Xun¹*, LIU Ying-Li¹, ZHANG Huai-Wu¹, LING Wei-Wei¹, XIE Yun-Song¹, XIAO John-Qiang²

2008, 29(3):  640-644.  doi:

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The polyaniline(PANI)-barium ferrite nanocomposite with magnetic behavior was synthesized by in situ polymerization of aniline in the presence of BaFe₁₂O₁₉ nanoparticles with 60—80 nm diameters. The structure, morphology and magnetic properties of the samples were characterized by powder X-ray diffraction(XRD), Fourier transform infrared(FTIR) spectrum, scanning electron microscopy(SEM), transmission electron microscopy(TEM) and vibrating sample magnetometer(VSM) technique. The results of spectroanalysis indicate that there was interaction between PANI chains and ferrite particles. The composite exhibited the hysteresis loops of the ferromagnetic nature. The saturation magnetization and coercivity of composite decreased greatly compared with barium ferrite. The absorbing bandwidth less than -20 dB is 15.07 GHz. And the polymerization mechanism and interactions in the nanocomposites were also discussed.

Studies on Coarsening of Microdomains in Binary Polymer Mixtures by Lattice Boltzmann Methods

SONG Kai-Xu^1,3, SUN Zhao-Yan¹*, AN Li-Jia¹, TONG Zhen²

2008, 29(3):  645-650.  doi:

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An improved free energy approach Lattice Boltzmann model(LBM) is proposed by introducing a forcing term instead of the pressure tensor. This model can reach the proper thermodynamic equilibrium after enough simulation time. On the basis of this model, the phase separation in binary polymer mixtures is studied by applying a Flory-Huggins-type free energy. The numerical results show good agreement with the analytic coexistence curve. This model can also be used to study the coarsening of microdomains in binary polymer mixtures at the early and intermediate stages. The simulation results are in accordance with those found in experiments. To understand the coarsening of microdomains at the late stage, we study the relationship between the growth exponent of the characteristic domain size and the interaction parameter χ and chain length N. The rescaled simulation results show that the growth exponent dependence on χ and N is trivial, while the growth exponent dependence on the fluid viscosity is dominant.

Relationship Between Solvated Polymer Peak and Solvent Peak Using Mixed Solvent as Eluents in Size-exclusion Chromatography

WANG Qing-Guo¹*, LI Xiao-Wen¹, LIU Bo¹, CAI Li-Xing¹ , CHENG Rong-Shi^2,3

2008, 29(3):  651-654.  doi:

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In Size-exclusion Chromatography(SEC) two peaks are often observed for polymer samples when solvent mixtures are employed as eluents. These two peaks are solvated polymer peak and free solvent peak respectively. Theoretical analysis shows that the peak area of the solvated polymer A₃^eff is actually the sum of the “naked polymer” peak area A₃ and the bound solvent peak area A₁*. A₁* is equal to that of the free solvent peak A₂* in magnitude but opposite in sign. In this study the data of A₃^eff, A₃ and A₂* were measured for the system of polystyrene(3)-chloroform(1)-methanol(2). The results support the analytical prediction and indicate that the preferential adsorption coefficient can be determined from either the polymer peak or the free solvent peak.

研究快报

Synthesis and Properties of Poly(aryl ether ketone) Macrocyclic Oligomer with Electroactive Groups

YANG Li-Guo, YAO Lei, WANG Yong-Guo, BEN Teng*, ZHANG Wan-Jin

2008, 29(3):  655-657.  doi:

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A new electroactive poly(aryl ether ketone) macrocyclic oligmer with phenyl-capped tetramer was synthesized by the modified pseudo-high-dilution method, whose structure with a rigid molecular backbone contains a cavity of well-defined size. The oligomer was characterized with mass spectrometry, IR and ¹H NMR, ¹³C NMR spectroscopies. Its redox property was checked by cyclic voltammetry and chemical oxidation process was monitored by UV spectroscopy. We found that it has a reversible electrochemical property like common oligoanilines. Combined with its well-defined structure, the oligmer is expected to act as a kind of host molecules which are capable of molecular recognition.

Interaction of Copolymer-Zn with Polypeptide

ZHAO Jian-Xin¹, QIAO Yi-Tao¹, FENG Jing¹, LUO Zhao-Feng², YUAN Zhi¹*

2008, 29(3):  658-660.  doi:

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A new copolymer(C) was designed and synthesized. Isothermal Titration Calorimetry(ITC) expe-riments showed the strong binding of C-Zn and the predetermined peptide sequences(DFLAE, appear in many peptides sequence which cumulate in serum of uremic patients). The further ITC experiments demonstrate that the binding is the result of the cooperative effect of coordination and hydrophobic interaction, which may provide further understanding on the mechanism of polymer-metal-peptide interaction and a structural basis for designing the adsorbents for the target peptide.