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Table of Content

    10 December 2010, Volume 31 Issue 12
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    Contents
    Cover and Content of Chemical Journal of Chinese Universities Vol.31 No.12(2010)
    2010, 31(12):  0. 
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    Cover and Content of Chemical Journal of Chinese Universities Vol.31 No.12(2010)
    2010, 31(12):  0. 
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    Volume Contents of Chemical Journal of Chinese Universities to Vol.31(2010)
    2010, 31(12):  1. 
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    Effect of Polyaspartic Acid Modification on Stability and MRI Enhancement of Magnetic Iron Oxide Nanoparticles
    SUN Lin LIU GuiFeng ZHUANG JiaQi ZHANG HuiMao YANG WenSheng
    2010, 31(12):  2313-2315. 
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    Polyaspartic acid (PSAP) was employed to modify the surface of superparamagnetic iron oxide (SPIO). The colloidal stability of SPIO could be adjusted by the amount of PSAP used and the modified SPIO showed improved stability under physiological condition. Magnetic resonance imaging (MRI) experiments of rabbit brain demonstrated that the PSAP modified SPIO can be well dispersed into the brain tissue, resulting in enhanced contrast of the MRI images.

    Letters
    Photo-generated Charges Characteristics of CdS/ZnO Heterostructures Materials
    WANG LingLing YANG WenSheng WANG DeJun XIE TengFeng
    2010, 31(12):  2316-2318. 
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    The photo-generated charges characteristics of CdS/ZnO heterostructures materials have been studied by means of Surface photovoltage techniques. The results showed that the photovoltage intensities of CdS/ZnO heterostructures materials decresed comparing with that of CdS. From the results of transient photovoltage measurement, the photo-generated electrons of CdS could transferr to ZnO under illumination since an electric field formed on the interface between CdS and ZnO. But this field is too weak to dominate the photo-generated charges characteristics. This result indicates that photo-generated charges characteristics can be clarified furthermore by means of surface photovoltage phase and transient photovoltage techniques.
    Selective Deposition of Silver Dendritic Structures and Its Catalytic Property
    WANG HaoNan QI DianPeng ZHAO XiaoJie MA RenPing YU JingSheng Lü Nan
    2010, 31(12):  2319-2321. 
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    Silver dendritic structures were electroless deposited on the top of silicon pyramids which were obtained by anisotropic etch in KOH solution. More details of the silver dendritic structures were observed by scanning electronic microscopy (SEM) and X-ray diffraction (XRD) were performed to further investigate the silver dendritic structures; the peaks observed are consistent with the JCPDS card (JCPDS No. 420783). Furthermore, the formation mechanism of silver dendritic structures has been clarified base on the model of galvanic cell and the diffusion-limited aggregation (DLA). The results show that the effect of point plays an important role in the selective deposition of silver dendritic structures. The silver dendritic structures can be used for catalytic reduction of 4-nitroaniline and this structures might be used for the micro-functional devices in the future.
    Articles
    Protection of ZnO Nanoparticles to Beauveria bassiana Conidia from Ultraviolet Radiation and Their Biocompatibility
    CHEN PeiRong WANG Bin YAO HongZhang LIN HuaFeng HUANG Bo LI ZengZhi
    2010, 31(12):  2322-2328. 
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    ZnO nanoparticles modified with oleic acid were prepared by chemical precipitation method, and their ultraviolet absorption properties and protection efficiency to Beauveria bassiana conidia in oil formulation were investigated. The mixture of ZnO nanoparticles and conidia were observed with SEM, and their biocompatibility was evaluated, based on significant difference levels which were analyzed by measuring germination percentage of conidia in formulation after storage. The results show that the obtained ZnO nanoparticles with particles size of 27nm had a strong absorption in the 200-370nm ultraviolet wavelength range. After 8-h exposure to xenon light，the protection efficiency of ZnO nanoparticles to conidia in oil formulation with 1.0% (mass fraction), 2.0% and 5.0% ZnO nanoparticles were over 60%, while the control group’s protection efficiency was 9.7%. A mass fraction of ZnO nanoparticles were absorbed on the surface of conidia and a coating layer that provided protection to conidia from UV degradation was formed. After 10-month room storage, there were no significant differences for conidia germination among four oil formulations containing 0.0%, 0.5%, 1.0% and 2.0% ZnO nanoparticles. As a result, ZnO nanoparticles had a good biocompatibility with Beauveria bassiana. The concentration of ZnO nanoparticles added to conidia oil formulation should be 1.0%-2.0%.
    Biomimetic Synthesis of Dendrite-shaped Aragonite Calcium Carbonate Particles and Application in PVC
    ZHAO LiNa WANG XiuYan KONG ZhiGuo WANG ZiChen
    2010, 31(12):  2329-2333. 
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    In the paper, the dendrite-shaped aragonite particles have been biomimetically synthesized through the carbonation route in the presence of polyacrylic acid (PAA). The as-prepared products were characterized with field emission scanning electron microscope (FESEM), X-ray diffraction (XRD) and fourier transform infrared spectroscopy (FT-IR). The effects of the reaction temperature and the concentration of PAA on the nucleation and growth of aragonite crystals were investigated. The possible growth mechanism of the dendrite-shaped aragonite particles was discussed. This research can open up a new avenue of industrial production of CaCO3 particles with exquisite and unique morphologies due to the preparation method employed by us is simple, low-cost and mild condition.
    Synthesis and Photoluminescence of β-SiAlON:Eu2+ Blue Phosphor
    LI YouFen LI Jie YANG JianLong
    2010, 31(12):  2334-2338. 
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    Blue β-SiAlON:Eu2+ phosphor was synthesized from Si, SiO2, AlN and Eu2O3 powders by metallothermic reduction-nitridation reaction. The influences of firing temperatures on compositions of β-SiAlON:Eu and photoluminescence were investigated by X-ray diffractometer and fluorescent spectrophotometer, respectively. The results indicate that excitation spectra of β-SiAlON:Eu2+ consists of two broad bands centered at 290 nm and 325 nm, and emission spectrum exhibits a single intense broad emission band at ~ 485 nm with 75 nm of half-peak width, which corresponds to 5d-4f transition of Eu2+. The critical concentration of Eu2+ is 8%. The mechanism analysis suggests that the energy transfer between the Eu-Eu ions occurs and the critical distance is 1.44 nm; Eu2+ occupies the space of tubular channel along [001] direction in the β-SiAlON crystal.
    Induced Synthesis of Monoclinic Hydroxyapatite by Chitosan and Structure Characterization
    XUE Bo SHI YunFeng HE ShuMei LI LanYing GUO ZhenZhao ZHANG LanLan LI Hong
    2010, 31(12):  2339-2343. 
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    Monoclinc hydroxyapatite nanocrystals have been successfully synthesized at room temperature. X-ray diffraction, ICP, Fourier transform infrared spectroscopy, transmission electron microscopy and high-resolution transmission electron microscopy was used to characterize the samples. The experimental results indicate that the as-synthesis samples are monoclinic hydroxyapatite, which synthesized before only at very high temperature. This is the first report of fabricating monoclinic hydroxyapatite crystals at low temperature environment.
    Synthesis, Crystal Structure and DNA Cleavage of a New Holmium(III) Nitrate with a Schiff-based Macrocyclic Ligand
    HU Xue-Lei
    2010, 31(12):  2344-2348. 
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    The title macrocyclic complex [Ho(H2L)(NO3)2](NO3) (H2L denotes the macrocyclic ligand, Fig. 1) has been synthesized and characterized by elemental analysis, infrared spectra, and electrospray mass spectra. Its crystal and molecular structures were determined by X-ray diffraction methods. The crystal crystallizes in the hexagonal system, space group P3(1)21 with a=1.47213(7) nm， c=2.8998(3) nm，α=90°，γ=120°，V=5.4424(7) nm 3，Z=6，R＝0.0331, wR＝0.0928。 The central holmium ion was located in one of the compartments of the macrocyclic ligand and was coordinated with two oxygen and three nitrogen atoms of the macrocycle. Two nitrates were chelated in the opposite positions of the macrocycle, and the third one is ionic. So the central ion presented a distorted tricapped trigonal prismatic coordination geometry. The preliminary studies of cleavage of double stranded DNA was demonstrated by electrophoresis gel.
    Synthesis and Properties of Copper Oxide Nanocrystals
    ZHAO LiYan, NING JiaJia, LIN AoLei, LI DongMei
    2010, 31(12):  2349-2353. 
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    CuO nanocrystals were prepared via hydrothermal synthesis route. The chemical composition and crystal structure and morphology were characterized by the X-ray diffraction (XRD), transmission electron microscope (TEM) and high resolution transmission electron microscope (HRTEM). The effects of CTAB, KOH and sodium citrate were investigated, and a formation mechanism of CuO nanoplates was proposed. The optical properties of CuO nanoplates were studied by UV-vis absorption spectrum, moreover, CuO nanoflowers showed high ratio surface, which have potential for catalysis material.
    Hemocompatibility of Carboxylic Graphene Oxide
    2010, 31(12):  2354-2359. 
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    Functionalization of Graphene oxide is important for technological applications since it allows integrating into different environments such as biological fluids, polymer matrices, silicon surface and others. Graphene oxide was made through the ultrasonic separation of graphite oxide, and then it was modified with functional group by chloroacetic acid, and finally, the graphene oxide modified with carboxyl groups was prepared. Compared with graphene oxide, the FTIR of GeneO-COOH showed a weaker -OH peak, a stronger -COOH peak, and a bigger peak width. FTIR showed partial epoxy and hydroxyl were activated into carboxyl. On TG spectrum, the main weight loss of GeneO-COOH showed condensation of -COOH groups in the form of a loss of structural water. The curve which reflected the kinetic profiles of recalcification time was changed from steep to gentle along with the increases of the consistency of GeneO-COOH. The recalcification time of GeneO-COOH was prolonged by 11 min at 1.25μg/mL, and the value of OD reduced by 8.14%. The hematolysis ratio was less than 5 % within the range of 0.5~100μg/mL. The anti-clotting property of GeneO-COOH was better than that of GeneO at the same low concentration. The improvement was mainly made by carboxyl group with a negative charge and direct complexation between carboxyl group and clotting factor. Hence, it may be conclude that GeneO-COOH may be suitable as biomaterials in the field of medical.
    Quantitative Analysis of Fluorescent Dye\|labeled DNA by High Resolution Inductively Coupled Plasma Mass Spectrometry
    GAO Yun-Hua, LI Hai-Feng, LI Jian-Xin, LI Peng,YE Jian, ZHAO Xing-Chun
    2010, 31(12):  2360-2365. 
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    The accurate mass determination method of fluorescent dye-labeled oligonucleotides by high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) was established. This method allows for the mass of fluorescent dye-labeled oligonucleotides to be traceable to the SI. The fluorescent dye-labeled oligonucleotides was processed by column chromatography、ultracentrifugation、dialysis。The purity was detected by electrophoresis chip and electrical conductivity。The fluorescent dye-labeled oligonucleotides was digested with microwave in nitric acid. The phosphorus from the fluorescent dye-labeled oligonucleotides was quantitative determined by the HR-ICP-MS. The parameters of HR-ICP-MS and microwave digestion was optimized. The interference factors of HR-ICP-MS such as physical interference, signal drift interference, isotopes, phosphorus element speciation interference was analyzed and corrected with ultra-filtration, internal standard of Y（88.906）, certified reference material of phosphate, nucleotide, oligo DNA. The uncertainty in measurement was evaluated mainly from method precision, Phosphorus CRM, Nitric acid digestion, Weight of sample and CRM. A uncertainty (< or = 8.28%) was smaller than ultraviolet spectrophotometry, fluorescence spectrophotometry and real time PCR. This method will aide in the development of Certified Reference Materials (CRMs) with certified nucleic acid（DNA、RNA） content.
    Aptamer-modified AuRu Nanoparticle Catalytic Resonance Scattering Spectral Assay for the Determination of Trace Pb2+
    LIANG Ai-Hui, ZHANG Jing, WEN Gui-Qing, LIU Qing-Ye, LI Ting-Sheng, JIANG Zhi-Liang*
    2010, 31(12):  2366-2371. 
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    The Au/Ru nanoparticle, in the mole ratio of 5/1, was modified by aptamer to prepare an aptamer AuRu nanoprobe (AptAuRu) for Pb2+, and the AptAuRu probe was stable in pH 7.0 Na2HPO4-NaH2PO4 buffer solution and in the presence of 85 mmol/L NaCl. Upon addition of Pb2+, the nanoprobe reacted with Pb2+ to form very stable G-quadruplex, and the released AuRu nanoparticles aggregated to big particles, which result to the resonance scattering (RS) peak at 592 nm increasing. The increased RS intensity was linear to the concentration of Pb2+ in the range of 1.2-240 pmol L-1. After filtration, the unreacted AptAuRu nanoprobe in filtration solution exhibited strong catalytic effect on the slow particle rection of NaClO3-NaI-TDMAC, and the association complex particle appeared a resonance scattering peak at 472 nm. When the concentration of Pb2+ increased, the amount of AptAuRu nanoprobe in filtration solution decreased, and the catalysis weak, that result to the resonance scattering intensity at 472 nm decreasing. The decreased intensity ΔI472nm was linear to the Pb2+ concentration in the range of 0.12～60 pM, with a regression equation of ΔI472nm =3.1C + 7.3 and a detection limit of 0.08 pM Pb2+. The RS assay was applied to analysis of Pb2+ in waste water, with satisfactory results.
    Microwave Assistant Synthesis Gold Nanoparticles and Their Application in Protein Determination
    SHAN Hong-Yan, LIU Dian-Jun, WANG Zhen-Xin
    2010, 31(12):  2372-2374. 
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    Herein, we report a novel microwave (MW) assistant method for gold nanoparticle synthesis. The formation of gold nanoparticles occurs rapidly in a single step, carried out by directly heating a reaction mixture of HAuCl4 with sodium citrate in an MW reactor. The particle size and size distribution was controlled by subtle variation of HAuCl4 to sodium citrate ratio. After functionalisation, the using of the as-prepared gold nanoparticles for protein determination was also demonstrated.
    Effect of Fog Process on the Size Distribution of Polycyclic Aromatic Hydrocarbons in the Atmospheric Aerosol PM10
    FAN Shu-Xian, HUANG Hong-Li, GU Kai-Hua, LI Hong-Shuang, ZHU Bin, ZHANG Hong-Liang, FAN Yang
    2010, 31(12):  2375-2382. 
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    Fractionating samples of atmospheric aerosol PM10, collected during a fog high frequency period, were determined for 16 priority Polycyclic Aromatic Hydrocarbons (PAHs). Result shows that the average mass concentrations of PM2.1 and PM9.0 in the near surface layer of the fog area increase sufficiently, and the diurnal concentration variation of PM2.1 are changed due to fog process. Before, during and after fog event, the 16 priority Polycyclic Aromatic Hydrocarbons (PAHs) in the PM10 mainly distribute in the fine particles with larger specific surface area, and averagely, 83.04% of PAHs distribute on the aerosol with Dp <2.1μm. During the fog event, the concentrations of ∑16PAHs in the particles (Dp: 1.1~2.1μm) increase remarkably, whereas those in the particles (Dp <0.65μm) decrease slightly; therefore, fog process plays a great role on the distributions of ∑16PAHs in the fine particles. In the daytime before, during and after fog event, the distributions of ∑16PAHs in the accumulation mode have large differences; the peak diameter of accumulation mode shifts to the larger size during the fog event, compared with those before and after fog. In a prolonged fog event, the peak diameter of daytime ∑16PAHs accumulation mode shifts to the larger size continuously and stays at 1.1~2.1μm, while there is no significant variation of peak diameter in the nighttime, all at 1.1~2.1μm; subsiquently, the size distributions of ∑16PAHs in PM10 are greatly affected by the duration of the fog event.
    Application of Accurate Mass and Elemental Composition Determination for Pesticides Identification Using a Unit Mass Resolution Gas Chromatography/Mass Spectrometry
    2010, 31(12):  2383-2389. 
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    On a unit mass resolution mass spectrometer, such as a single quadrupole MS, allowing for only rough mass confirmation for qualitative analysis. In this study, a novel mass spectral calibration technique, MSIntegnityTM implemented in MassWorksTM, is introduced to externally calibrated using a unique procedure that corrects for both mass axis and mass spectral peak shape to facilitate pesticides identi?cation with high mass accuracy, MS data were acquired in pro?le mode on a unit mass resolution single-quadrupole instrument, even at such a unit mass resolution on a true chromatographic time scale, will now enable the elemental composition determination of unknown ions or ion fragments using a conventional mass spectrometer. This identification capability is further enhanced by a uniquely accurate approach for elemental composition determination through the use of isotope distribution information, CLIPSTM.
    Preparation and Purification of Velvet Antlers Peptides and Its Antioxidant Activities
    WANG Hua, HUANG Yi-Bing, GAO KE-Xiang, SUN Hui, GAO Zhong-Li
    2010, 31(12):  2390-2395. 
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    An industrial alkaline protease Alcalase was used to hydrolyze the fresh velvet antler of sika deer (Cervus Nippon Temminck). The conditions of enzymatic hydrolysis were optimized. The effects of several factors, including amount of the enzyme, substrate concentration and hydrolysis time, on the antioxidative activities of the hydrolysis product were examined by orthogonal test design. The optimum hydrolysis conditions were established to be the amount of enzyme, 1:150; the substrate concentration, 1:13; hydrolysis time, 60min. The crude velvet antlers peptides were prepared by fractionation of ammonium sulphate. An elution peak with high antioxidative activities from Sephadex G-25 column chromatography of the crude velvet antlers peptides was collected and named as VAP-B. Finally, a further purified velvet antlers peptide component (VAP-B1) with molecular weight distribution from 200-800 was obtained from VAP-B by preparative HPLC. The protein content of VAP-B1 was 70.45%. An analysis of amino acid composition was also carried out. The antioxidative activities of velvet antlers peptide component (VAP-B1), including removal of superoxide anions, hydroxyl radicals and inhibition of lipid peroxidation were examined. The reducing power of VAP-B1 was also tested. The experimental results indicate that when VAP-B1 concentration was 20 mg/ml, the inhibition ratio to pyrogallic acid autoxidation reached to 91.9%, having a strong ability to scavenge superoxide anion; when VAP-B1 concentration was 10 mg/ml, the clearance rate to hydroxyl radical was 100% and was dosage-dependent in a certain rage of concentration; At the same time, VAP-B1 showed some capability of inhibition of lipid peroxidation and reducing power.
    New Method for the Preparation of Azoxybenzenes
    LIU Yu-Fang, LIU Bo, DONG Zhen-Ming, JIN Shuo, LIANG Cai-Yun, ZHU Rui-Tao, LU Yun
    2010, 31(12):  2396-2399. 
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    azoxybenzenes are important intermediates in fine and industrial chemistry, and applied in dyes, indicators and liquid crystals. In this paper we described a new method for preparing azoxybenzenes, nitroarenes were reduced to the corresponding azoxybenzenes by β-CD / NaOH in water. This method is simple, economic, environmentally friendly.
    Synthesis,Structures and Anti-tumor Properties of Capsaicin Analogues
    WANG Wen-Long, HUANG Yan-Lan, HU Wei-Xiao, SHAN Shang
    2010, 31(12):  2400-2406. 
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    Capsaicin is a natural product existing in the fruit of capsicum, which has been used for centuries for its medical effects. Modern research showed that capsaicin exhibits anti-proliferative activities against tumor cells. For the reason of studying the structure-activity relationship of capsaicin molecule, fifteen capsaicin analogues comprising the segment of vanillylamine acylamide were designed and synthesized from carboxylic acid or acyl chloride via the acylation and amidogen reactions. Their structures were characterized by IR, MS and 1H NMR techniques. The crystal structures of compounds W5 and W11 were determined by X-ray diffraction analysis. The anti-tumor properties of capsaicin analogues were evaluated against four different tumor cell lines by an MTT assay. The results suggest that the vanillylamine acylamide-containing compounds exhibit anti-proliferative activities against selected tumor cells. The inhibition rates against HELA , SMMC-7721, KB and HO-8901 of compound W1 have all reached greater than 90 % at the concentration of 100 μg/mL. The inhibition rates against KB and HO-8901 of compound W13 have respectively reached 89.62 % and 90.36 % at the concentration of 100 μg/mL. Preliminary structure-activity relationship analysis indicates that the segment of vanillylamine acylamide is an active group in anti-tumor process.
    Sulfation of a Squid Ink Polysaccharide and Its Anticoagulant Activities
    CHEN Shi-Guo, LI Zhao-Jie, WANG Yu-Ming, LI Guo-Yun, SUN Bei-Bei, XUE Chang-Hu
    2010, 31(12):  2407-2412. 
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    Abstract: This paper is the firstly reported the preparation, characterization, and anticoagulant activities of a chemically sulfated polysaccharide isolated from the ink of the squid, Ommastrephes bartrami. The squid ink polysaccharides (SIPs) were firstly sulfated with the pyridine-sulfur-trioxide complex in dimethyl sulfoxide. Structural characterization of sulfated SIP using nuclear magnetic resonance indicated that sulfation mainly occurred at the 4, 6-position of GalNAc. Further anticoagulant activity assay indicated that sulfated SIPs prolonged the APTT and PT times obviously. By evaluating their influence on anti-thrombin and anti-FXa activities mediated by antithrombin III and heparin cofactor II, the sulfate SIP TBA-1 obviously inhibited the activity of FIIa and FXa.
    Synthesis and Biodistribution of  125I-DMAIBZM for Dopamine D2 Receptor Imaging
    LI Guang-Hui, SHENG Xu-Jing, ZHU Jian-Hua
    2010, 31(12):  2413-2418. 
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    To improve the brain uptake of the benzamide compound 125I-AIBZM (S)- 5-125I -N-(1-ethyl-2-pyrrolidinyl) methyl-4-amine -2-methoxy- benzamide, the structure modification was performed resulting in a new compound 125I-DMAIBZM ((S)-5-125I-Iodo-N-(1-ethyl-2-pyrrolidinyl)methyl-4-dimethyl- amine-2-methoxy-benzamide) produced. Labeling was achieved by Iodogen method, with 74% radiochemical yield. After HPLC purification, radiochemical purity >99% was obtained. The receptor binding affinity of DMABZM to rat brain membrane（IC50为2.9589×10-7 mol?L-1）have shown high affinity to dopamine D2 receptor. The mice biodistribution data for 125I-DMAIBZM (the ratio striatum/cerebellum>6.5) indicates a good distribution in striatum with high specificity and affinity. The lipophilicity of 125I-DMAIBZM is significantly higher than that of 125I-AIBZM. Conclusion: 125I（123I）-DMAIBZM is in a promise state for Dopamine D2 receptor Imaging.
    3D-QSAR Study of N-Nitro Urea Derivatives with Herbicidal Activity
    SHEN Xiao-Xia, XU Sheng-Zhen, CHEN Chang-Shui
    2010, 31(12):  2419-2424. 
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    The preliminary bioassays indicated that N-nitro urea derivatives possess good activity against A. retroflexus L and S. sudanenses. To design the highly active title compounds, comparative molecular field analysis (CoMFA) was applied to study of the three-dimensional quantitative structure activity relationship (3D-QSAR) on 38 N-nitro urea derivatives. The reasonable models with predictive ability were obtained from the investigation (A. retroflexus L: q2=0.674, r2=1.000, R2pred=0.9989) and (S. sudanenses: q2=0.635, r2=1.000, R2pred=0.9958). The steric and electronic contour maps show that bulky and electropositive groups inked to 2, 5-position of N'-phenyl ring, electronegetive groups to 3-position, small and electronegetive groups to 4, 6-position may increase the herbicidal activity against A. retroflexus L, and also bulky and electronegetive groups to 2-position, small and electronegetive groups to 3-position, bulky and electropositive groups to 4-position, bulky groups to 5-position may increase the activity against S. sudanenses.
    Interaction of the Cucurbit[n]uril(n=6—8) with Buflomedil
    YANG Xiao-Na, JIANG Song, LI Xin-Jian, ZHU Wei-Guo, KANG Jian-Xun, ZOU Da-Peng
    2010, 31(12):  2425-2430. 
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    The host-guest chemistry of systems containing Buflomedil (denoted as DLDE) and cucurbit[n]uril (denoted as CB[n], n=6, 7, 8) is investigated by 1H NMR, ESI-MS, IR, and UV-vis spectra. The Buflomedil guest and CB[n], n=6, 7, 8 host can form a stable 1:1 inclusion complex, in which the position of the host is different, respectively. It was found that the size of the cavity of the CB[n] plays an important role in the interaction between the host and the guest.
    Theoretical Study on the Reaction Mechanism of Hydrolysis Process of Asymmetric trans-[Pt(Ⅱ)Cl2(#em/em#-pra)(hmp)] Complex
    YE Bing, XU Xuan
    2010, 31(12):  2431-2437. 
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    The hydrolysis process of the anticancer drug trans-[Pt(Ⅱ)Cl2(i-pra)(hmp)](i-pra= isopropylamine, hmp= 3-(hydroxylmethyl)-pyridine) with steric hindrance has been investigated by density functional theory at PBE1PBE level and CPCM model. The results exhibited that water molecules attack the Pt and Cl atoms perpendicularly to the quadrangular coordinate plane of Pt due to the steric effect. The hydrolysis is the synergistic effect of the H, O, Cl and Pt atom, acting as the 3p(Cl)→σ*(H-O), 5d(Pt)→σ*(H-O), LP(O)→LP*(Pt) and LP(O)→σ*(Pt-Cl) delocalizations. The transition state is an approximate trigonal-bipyramid geometry. In the processing of hydrolysis, the delocalization effect and the strength of Pt-O bond increase, while the strength of Pt-Cl bond decreases. Due to the solvent effects, energies of every reactant, transition state and product of the first and second hydrolysis are 63.6~386.3 kJ/mol lower than those of the gas phase, and the single-point energy barriers are 17.1~36.2 kJ/mol lower than those of the gas phase. The hydrolysis process is easier in the opposite direction of isopropyl with less steric hindrance. 1B and 2B are the dominant reaction paths of first and second hydrolysis, their enthalpy barrier (ΔH°298(aq)) are 79.7 kJ/mol and 87.8 kJ/mol respectively, which are higher than those of trans-[PtCl2(i-pra)2]. Moreover, the enthalpy barrier of second hydrolysis is much higher than cisplatin.
    Theory Study on the Distorted Structure and Stability of Copper\|Zinc\|Aluminum Layered Double Hydroxides
    NI Zhe-Ming, YAO Ping, LIU Xiao-ing, WANG Qiao-iao, XU Qian
    2010, 31(12):  2438-2444. 
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    We proposed a periodic interaction model for the layered double hydroxides, CuxZn3-xAl-LDHs. Based on density functional theory, the geometry of CuxZn3-xAl-LDHs was optimized using the CASTEP program. Jahn–Teller effect and the stability was investigated by analyzing the geometric parameters, hydrogen-bonding, charge populations, and binding energies. Results showed that the structure of staggered arrangement of Cu2+ and Zn2 + in the layer was relatively stable. As the amount of Cu2+ substituted Zn2 + in the layer increased, the symmetry of unit cell became weaker, and Jahn–Teller effect of the copper had little effect on the central Al3 +. The strength of electrovalent bond became stronger while the strength of covalent bond became weaker with the increase of Cu2+ substituted Zn2 + in the layer, so the covalent crystal of CuxZn3-xAl-LDHs transited to the ionic crystal gradually. The distortion caused by Jahn–Teller effect made an enhanced supermolecular interaction between the host layer and the guest, the strength of electrostatic interactions became weaker while the strength of hydrogen-bonding became stronger, and hydrogen-bonding was superior to the electrostatic interaction. In general, the absolute value of he binding energy decreased gradually with an increase in the number of Cu2+, then the chemical stability of the system got worse, and it was significant for synthesis of Cu-LDHs.
    Effect of Interactions Among Flooding Chemicals on Interfacial Properties of Adsorption Film
    2010, 31(12):  2445-2452. 
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    The dilational viscoelastic properties of Gemini surfactant C12COONa-p-C9SO3Na, partly hydrolyzed polyacrylamide, hydrophobically modified polyacrylamide were investigated at the decane–water interface by means of interfacial tension relaxation. The effects of different type electrolytes and ionic strength on interfacial dilational properties were exploited. The dilational elasticity and dilational viscosity are calculated at different frequencies and the relaxation processes were discussed by plotting cole-cole curves. The experimental results show that in-film molecular reorientation process and molecular diffusion-exchange between the interface and the bulk are two main processes controlling the nature of film. The increase of surfactant concentration will enhance molecular reorientation process, while molecular diffusion-exchange process will dominate adsorption film at low frequency. The influences on dilational properties of surfactant film depend on structure of polymer, ionic strength and ionic type.
    Influence of Monomer Molar Ratio on the Growth of PbSe Nanoparticles
    LI Yan, LIN Ao-Lei, LI Dong-Mei
    2010, 31(12):  2453-2457. 
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    In order to study the influence of Pb to Se monomer molar ratio on the growth of PbSe QDs, we synthesized PbSe nanopatical with different mole ratio of Se to Pb monomer. It indicates that the more Se monomer existed in the initial stage, the faster the nucleation process occurred, but slow the growth of nanoparticles. One reason is Se monomer is more active than the Pb monomer. The other reason is the special PbSe nanoparticle theory model.
    Influence of Activation/Deactivation Process on the Dynamics of Surface Initiated Polymerization with High Grafting Density
    LIU Yu-Hua, LI Min, LIU Hong, Lü Zhong-Yuan, ZHANG Zuo-Guang
    2010, 31(12):  2458-2462. 
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    The surface initiated polymerizations with different polymerization rate and different ratio of the transformation (activation/deactivation) probability under high grafting density are investigated using molecular dynamics simulation method. We find that polymerization rate and the ratio of activation/deactivation process greatly determine the properties of polymer brushes. By modifying the polymerization rate and tuning activation/deactivation process, we can obtain the polymer brushes with low polydispersity index in relatively short time.
    Mechanism of Photoinduced Formation Fucoxanthin Radical Cation in Organic Solvents
    YANG Fan, WANG Tian-He, WANG Peng, HAN Rui-Min, AI Xi-Cheng, ZHANG Jian-Ping
    2010, 31(12):  2463-2467. 
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    Kinetics of fucoxanthin radical cation (Fuc??) formation in chloroform and in methanol were comparatively studied by means of nanosecond time-resolved absorption spectroscopy combined with spetroelectrochemistry. Direct photoexcitation and anthracene-sensitized triplet excitation, respectively, were used to initiate the photochemistry of different fucoxanthin solutions. It was found that in chloroform Fuc?? was mainly formed from the singlet excited state of Fuc (S2), whereas in methanol it was mainly formed from the lowest triplet excited state of Fuc (T1).
    Effects of Li2CO3 Additive on the Performance of Graphite Electrode
    TIAN Lei-Lei, ZHUANG Quan-Chao, WANG Rong, CUI Yong-Li, FANG Liang, QIANG Ying-Huai
    2010, 31(12):  2468-2473. 
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    Effects of Li2CO3 additive on the electrochemical performance of graphite electrode was investigated by EIS and CV. The CV results showed that electrochemical performance of the graphite electrode was improved due to that the single electron reduction of EC during the first lithiation was largely suppressed in the electrolyte with Li2CO3. EIS results displayed that the SEI film showed better viscoelasticity in the electrolyte with Li2CO3, thus it can well accommdate the tiny volume change resulted from the process of Li-ion intercalation, which made Li-ion intercalation much easier.
    Synthesis and Characterization of PANI/PS Composite Prepared by in-situ Solution Polymerization
    ZHU Hong, LI Sheng-Song, KUANG Sheng-Lu
    2010, 31(12):  2474-2481. 
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    PANI was prepared via in-situ solution polymerization in the solvent system of alcohol (or ketone)-water, using DNSA as doping agent. PANI/PS composite were obtained by the solution blend. The products were characterized by TEM, FTIR, elementary analysis and TG. The result showed that the maximum conductivity of PANI doped with DNSA is 0.65 S/cm and higher than PANI doped with DBSA. The surface resistivity of composite is adjustable within a certain range and the minimum of it is 101Ω/□. It can be used for electromagnetic shielding and it is applicable to polymer surface.
    Preparation and Characterization of Hydrophobic Microporous Silica Membranes Modified by Phenyl Groups
    LI Zhen-Jie, WEI Qi, WEI Na-Na, LI Qun-Yan, NIE Zuo-Ren
    2010, 31(12):  2482-2487. 
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    Silica membranes modified with phenyl groups were synthesized through the acid-catalyzed co-hydrolysis and condensation reaction of tetraethyl orthosilicate(TEOS) and phenyltriethoxysilane(PTES). The pore structure and hydrophobic property of the modified silica membranes were characterized by SEM，means of nitrogen adsorption, water contact angle measurement, TG and FT-IR. The single gas permeation and permselectivity of the hydrophobic silica membranes were also investigated at room temperature. The results show that the hydrophobic property of the modified silica membranes has been gradually enhanced with increasing amount of PTES in the mixture. When the molar ratio of PTES/TEOS increases to 0.6 and H2O/TEOS to 9.6, the modified silica membranes exhibit an excellent hydrophobic property with a water contact angle of 115?0.5° and a desirable microporous structure with a pore volume of 0.17 cm3/g and a sharp pore size distribution centered at 0.4-0.5nm.The modified silica membranes conform to a combination of a surface diffusion mechanism associated with micropores and a Knudsen diffusion mechanism related to the larger pores or microcracks, with a H2 permeance of 1.49×10-6mol?m-2?Pa-1?s-1 and a permselectivity of 4.64 for H2/CO2 and 365.69 for H2/SF6.
    Study on Enzyme Mimics of Molecularly Imprinted Microgels
    WANG Hong-Fei, TANG Chun-Yan, YANG Hao, ZHANG Li-Ming
    2010, 31(12):  2488-2493. 
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    Molecularly imprinted microgels (MIGs) exhibiting selective esterase activity were prepared by a reverse emulsion method using maleic anhydride esterified dextran-aminopyridine conjugate (Dex-MA-AP) as the functional macromonomer, p-nitrophenyl phosphate (NPP) as the stable transition state analogue (TSA) and Co2+ as the coordination center. The interaction between Dex-MA-AP and NPP was investigated by UV adsorption spectra. The morphology and size of MIGs were observed by scanning electron micrographs (SEM). It was found that the catalytic activity of MIGs was greatly influenced by the amounts of the template and cross-linking agent. The hydrolysis kinetics of p-nitrophenyl acetate (NPA) in the presence of MIGs could be described by the Michaelis-Menten equation. The maximium velocity (Vm) and Michaelis-Menten constant (Km) were found to be 25.1 mmol/h and 0.030 mmol/L, respectively. In addition, the MIGs was found to show high catalytic selectivity to NPA.
    Synthesis and Characterization of Reticulated Structure Ammonium Polyphosphate with Crystal Form V
    CHEN Wen-Yan, LIU Xin-Chun, LIU Gou-Sheng, YU Jian-Guo
    2010, 31(12):  2494-2499. 
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    Ammonium polyphosphate (APP) with reticulated structure was prepared by heating a mixture of 85% food grade phosphoric acid and melamine under wet ammonia atmosphere. Its water-solubility, XRD, 13C NMR, FTIR and TG were investigated, and compared with those of APP-I and APP-II. Results show that this product has excellent water-resistence, its XRD spectrum is similar to that of APP-V in literature, its 13C NMR and FTIR spectra show that this product is a cross-linked and reticulated structure of ammonium polyphosphate chains with triazine ring as basebone. TG tests show that the residual weight at 700℃ for this product is 53.6% , higher than 40.29% for APP-I and 36.18% for APP-II, meaning its excellent thermal stability at high temperature.
    Aggregation Behavior of Tetrakis(4-sulfonatophenyl)porphyrin in the Inner Water Pool of Inverse Microemulsions
    ZHANG Li-Yan, LI Yan, ZHAO Li-Zhi, LIU Xue, WANG Xin, MA Ru-Jiang, AN Ying-Li, SHI Lin-Qi
    2010, 31(12):  2500-2505. 
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    TX-100/n-hexanol/water/cyclohexane inverse microemulsions have been used to entrap tetrakis(4-sulfonatophenyl)porphyrin (TPPS). The aggregation behaviors of TPPS in the inner phase of nonionic W/O inverse have been investigated on changing pH, size of the microemulsions water pool and the concentration of porphyrin. The apparent pKa of TPPS in microemulsions have been found to be much lower than that in open aqueous solution, and exhibit a decrease on decreasing the water pool dimension. Deprotonized TPPS was prevalently presented when pH > pKa. While J-aggregates and protonized TPPS are the main species existed when pH < pKa, and more protonized TPPS self-assemble into J-aggregates on increasing the concentration of TPPS. At fixed pH, the deprotonized TPPS tend to become protonized and self-assemble into J-aggregates on increasing the inner water pool dimension.
    Enhancing Antifouling Property of Polysulfone Ultrafiltration Membrane by Grafting Poly(ethylene glycol) Methyl Ether Methacrylate(PEGMA) via UV\|initiated Polymerization
    YU Hai-Jun, CAO Yi-Ming, KANG Guo-Dong, ZHOU Mei-Qing, LIU Jian-Hui, YUAN Quan
    2010, 31(12):  2506-2510. 
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    Abstract: Poly (ethylene glycol) methyl ether methacrylate (PEGMA) was grafted onto polysulfone (PSF) ultrafiltration membrane using benzophenone (BP) as the initiator to improve the antifouling property. Polymer chain scission was suppressed by H-abstraction from methyl groups under long-wavelength UV irradiation (λ﹥300nm), which partly avoided the photodegradation of PSF ultrafiltration membrane. The effects of PEGMA concentration, UV irradiation time and BP concentration on grafting degree and the improvement of membrane antifouling properties were investigated. Attenuated total reflectance fourier transform infrared spectroscopy (ATR/FTIR) was used to characterize the change of chemical composition. Static contact angle (CA) measurements showed that the hydrophilicity of PEGMA-modified PSF membranes was enhanced with the increase of grafting degree. The flux of pure water decreased slightly after modification, while the rejection to bovine serum albumin (BSA) increased. The improvement of antifouling property for PEGMA-modified membrane was accordant with the increase of grafting degree. The excellent antifouling property indicated PEGMA-modified membranes a potential application in ultrafiltration process.
    Fabricating Polymer Superhydrophobic Surface by Porous Spherical CaCO3 Particle Layer as Template
    ZHONG Ming-Qiang, ZHENG Jian-Yong, FENG Jie
    2010, 31(12):  2511-2517. 
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    A novel phenomena or surface microstructure formation mechanism was found during fabricating superhydrophobic polymer films by replica-molding method using porous spherical CaCO3 particle layers as templates. Briefly, polystyrene sulfonate (PSS) doped porous spherical CaCO3 particle suspension was first cast onto a glass substrate and dried towards forming a thin layer of particles. Then low-density polyethylene (LDPE) pellets were bestrewed onto such a CaCO3 particle layer. After the LDPE was heated to melt status (180 oC), another piece of glass plate that had been pre-heated was covered on the LDPE melt for 10 min and then clamped together (3.5 kPa) with the glass substrate bearing the CaCO3 particle layer. After being cooled, peeled off from the glass substrate and rinsed with flowing water, the LDPE surface enwrapping porous spherical CaCO3 particles was obtained. Then it was further etched in 20 wt% HCl solution for 10 min. After washing and drying, the LDPE film with superhydrophobic surface was created, with water contact angle up to (152.8±2.5)o and sliding angle about 6o. Moreover, such superhydrophobicity was confirmed stable to continuous 30 μL water droplets free falling from 100 cm height. SEM imaging showed that completely different with honeycomb structures that were generally formed by using soluble spherical particles as replica templates, conglutinated spherical particles structure were found on the LDPE surface. Moreover, nano structures were also found on each single spherical particle surface. Element characterizations by EDS and XRF both demonstrated that no Ca element existed on or blow herein microstructured LDPE surface. To elucidate the formation mechanism of conglutinated spherical particles structure, the LDPE smooth surface was first covered with sparse porous spherical CaCO3 particles, then heated to melt state and held for 30 min. After being cooled and thoroughly etched with HCl solution, the LDPE surface presented lotus seedpod like structure, e.g., smaller spheres staying within larger holes. Such phenomena demonstrated that it was the spontaneous loading of hydrophobic melt LDPE macromolecules into PSS walled nano pores of CaCO3 particles that formed conglutinated spherical particles structure on LDPE surface. This find not only supplies a new method for fabricating polymer superhydrophobic films but also develops a novel strategy for expanding applications of porous spherical CaCO3 particles.
    High Effective Ring-open Polymerization of ε-Caprolactone Catalyzed by Bicycolopentadienyl Samarium(Ⅱ) Complex (C5H5)2Sm(THF)
    QI Min-Hua, JIA Hui-Fang, LIU Zhi-Sheng, SHEN Qi, SHEN Zhi-Quan
    2010, 31(12):  2518-2520. 
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    Lanthanide (II) complex (C5H5)2Sm(THF) applied in catalyzing the polymerization of ε-caprolactone was investigated. The results indicated that the complex as single component catalyst showed very high activity and the number-average molecular weight of the polymer gained was also very high. For example, when the molar ratio of catalyst to monomer was 1/5000, the conversion could still reach 50.3% and the number-average molecular weight of the polymer gained was as high as 32.4?104. The conversion of the polymerization and the number-average molecular weight of the polymers were affected by temperature, time of polymerization and use level of catalyst in polymerization process. The number-average molecular weight of the polymer decreased, the molecular weight distribution was slightly wide, but the conversion increased as the polymerization temperature increasing. The conversion increased and the number-average molecular weight decreased as the dosage of catalyst increased. The molecular weight distribution of polycaprolactones gained were narrow. The number-average molecular weight and molecular weight distribution of polycaprolactone were measured by GPC.
    Synthesis of Amphiphilic Block Copolymer PCL-b-PDMAEMA by the Combination of Enzymatic-promoting Polymerization with ATRP and Its Self-assembly Behavior
    LIU Lin-Lin, WANG Shu-Wei, LI Ya-Peng, SA Zong-Peng, ZHU Ming, PAN Si, YANG Yan-Ming
    2010, 31(12):  2521-2524. 
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    Abstract: Amphiphilic poly(caprolactone)-block-poly(dimethylaminoethyl methacrylate) (PCL-b-PDMAEMA) is synthesized utilizing a chemoenzymatic approach. The structure, molecular weight and its distribution of the resultant are characterized by H-1 Nuclear Magnetic Resonance (1H NMR), Fourier Transfer Infrared Spectra (FT-IR), Gel Permeation Chromatography (GPC). The properties of the solution of the resultant is studied, suggesting an increased tendency of forming micelle in aqueous media with a higher proportion of hydrophobic segments in the polymer, demonstrating a decreased Critical Micelle Concentration and higher thermodynamic stability. Previous studies indicate that PDMAEMA is responsive to temperature and pH, having various configurations in different temperature and pH: average hydraulic diameter increases with a decreased pH and/or decreased temperature.
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