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Table of Content

    10 May 2010, Volume 31 Issue 5
    Contents
    Cover and Content of Chemical Journal of Chinese Universities Vol.31 No.5(2010)
    2010, 31(5):  0. 
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    Review
    Colloidal Lithography——Construction and Application of Nanostructured Surfaces
    ZHANG Gang*, ZHAO Zhi-Yuan, WANG Da-Yang
    2010, 31(5):  839-854. 
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    Combining “top-down” patterning with “bottom-up” self-assembly as template colloidal lithography provides a unique patterning strategy. Spontaneous formation of well-ordered colloidal arrays provides lithographic masks or scaffolds for creating useful patterns. Based on self-assembly of colloidal spheres as template, the controlled “positive” deposition of nanoparticles and “negative” etching processes could be used for the fabrication of nanostructured materials, ranging from several tens of nanometers to micrometer scales for 2D and 3D ordered architectures. The feature size can easily shrink below 100 nm by reducing the diameter of the microspheres used according to the simple correlation between the interstice size and the sphere diameter. The feature shape can be easily diversified by the crystalline structure of a colloidal crystal mask, the time of anisotropic etching of the mask, the incidence angle of the vapor beam and the mask registry. Colloidal lithography provides a complementary tool for conventional and fully “top-down” lithographic techniques, and thus holds immense promise in surface patterning. They show versatility applications such as biosensors or chemosensors using for detection tool. Colloidal lithography is also suitable for modifying surface properties which is useful for emerging applications in biotechnology and chemically and structurally designed interactive sites for the attachment.

    Letters
    Aggregation Induced Luminescence in the Λ-Shaped iso-Phoronederivative Nanoparticles
    ZHENG Jing-Jing, WANG Lei*, LIU Yang, TAO Xu-Tang*
    2010, 31(5):  855-857. 
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    A novel Λ-shaped compound DMCEM based on Tröger′s base was designed, synthesized and its photophysical properties were examined in detail. DMCEM exhibited an aggregation-induced emission enhancement(AIEE) effect and emitted strong red fluorescence in solid states and faint fluorescence in the dilute solution. Nanocrystals of DMCEM ranging from 60 to 160 nm with well-defined spherical shape were prepared. The DMCEM naoparticles possess special size dependence on their optical properties. The red shift of the absorption and the blue shift of the emission with the increase in the particle size may be attributed to the increased rigidification of the crystal lattice and the associated decrease of vibrational relaxation.

    Photo-generated Charge Transfer Characteristics of n-Si/TiO2/Azo Pigment in Micrometer Regions
    WANG Xue-Song, WANG Ling-Ling, WANG De-Jun, XIE Teng-Feng*
    2010, 31(5):  858-860. 
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    The photo-generated charge transfer characteristics of n-Si/TiO2/Azo pigment in micrometer regions was studied by means of kelvin probe force microscopy(KFM) technique. The results showed that the photo-generated electrons of Azo pigment particles transferred to n-Si/TiO2 under illumination, and a photo-induced p-n-p structure in micro-scale was observed for the first time. This result indicates that photo-generated charge transfer characteristics of organic/inorganic complex in nano-scale can be observed directly by KFM.

    Effect of [C14MIM]Br Ionic Liquid on Foaming Behavior of Polypropylene by Supercritical CO2
    LI Bo-Xuan , YU Jian*, DING Yun-Sheng*, ZHANG Jun, HE Jia-Song
    2010, 31(5):  861-863. 
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    Effects of an ionic liquid, 1-n-tetradecyl-3-methylimidazolium bromide([C14MIM]Br), as a foaming additive on the foaming behavior of polypropylene(PP) by supercritical CO2 technique was reported. Mass ratio of PP/[C14MIM]Br up to 100∶10 was incorporated via melt blending. The melting behavior and fractured morphology of PP/[C14MIM]Br samples were investigated by differential scanning calorimetry(DSC) and scanning electron microscopy(SEM), respectively. The CO2 sorption was measured by commonly accep-ted gravimetric method. The results of DSC and CO2 sorption experiments show that [C14MIM]Br has little effect on the crystallinity, melting point and the mass uptake of CO2 of PP. SEM images reveal that [C14MIM]Br forms a well-dispersed phase, whose size increases with [C14MIM]Br content, in the PP matrix. The foamed PP/[C14MIM]Br samples exhibit close cell structure, increased cell size and decreased un-foamed region and bulk density, compared with pure PP foamed under the same saturation conditions of 155 ℃/10 MPa, indicating ionic liquid [C14MIM]Br has significant effect on the foaming behavior of PP.

    Janus Particles Prepared by Pickering Emulsion Template
    WANG Chao-Yang*, YANG Rui, CHEN Yun-Hua, TONG Zhen
    2010, 31(5):  864-866. 
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    “Semi-decoration” of silica particles(so-called Janus particles) with polydimethylamino ethylmethacrylate(PDMAEMA) grafts was carried out using surface-initiated atom transfer radical polymerization(SI-ATRP) based on Pickering emulsion template. ATRP initiator-immobilized silica particles assembled at the interfaces of paraffin oil-in-water emulsions and an ultimately stable Pickering emulsion was formed. SI-ATRP of water-soluble monomer DMAEMA was conducted in the water phase of the Pickering emulsion from the outer side of silica nanoparticles. Janus particles were obtained. Ag nanoparticles absorbed onto the PDMAEMA region of silica particles could be observed by transmission electron microscopy(TEM) image which indicated that Janus particles were successfully prepared. The semi-decoration by SI-ATRP based on Pickering emulsion technique offers a new route to designing Janus particles.

    Articles
    Syntheses, Structures of Four New Complexes Constructed by Flexible Pyridine Ligand and the Relationship Between Conformations and Structures
    JI Chang-Chun, XU Zheng-Jiang, LI Jing, LIU Guang-Xiang, ZHENG He-Gen*
    2010, 31(5):  867-873. 
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    Four new complexes [Co(pcaede)2Cl2·2CH3CN·H2O]n(1), [Co(pcaede)2Cl2·H2O]n(2), [Hg(pcaede)I2]n(3) and [Hg(pcaede)Br2]n(4) were prepared with a flexible ligand 3-pyridinecarboxylic acid 1,2-ethanediyl ester(pcaede) and Co/Hg salts. They were characterized by elemental analysis, IR and X-ray single-crystal diffraction. Complexes 1 and 2 both have an one-dimensional(1D) chain sturcture with channels. Complex 3 processes a 1D meso-helix sturcture, and complex 4 exhibits a 1D infinite zig-zag chain structrue. The results demonstrated that the solvent molecules filled in channels and counteranions have a significant impact on the assembly of the complexes. Moreover, theoretical calculations were carried about the conformation of the ligand in four complexes.

    Preparation of CdSe/CdS/SiO2 Nanospheres and Their Luminescent Properties
    MA Xiao-Bo, NIE Wei, WANG Ce, ZHANG Wan-Jin*, JI Xiang-Ling
    2010, 31(5):  874-880. 
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    Luminescent CdSe/CdS core-shell quantum dots were synthesized by two-phase method. These CdSe/CdS quantum dots are encapsulated with silica spheres from hydrolysis of tetraethylorthosilicate(TEOS) in the presence of ammonium. Adjusting the amount of quantum dots and ammonia, the reaction temperature and time as well as ratio of solvents, the size of as-prepared CdSe/CdS/SiO2 nanospheres can be tuned in the range of 23—145 nm. The samples are characterized by TEM, UV-Vis, and fluorescence spectrometer, respectively. The highest quantum yield(QY) of the CdSe/CdS/SiO2 sample can reach 8.0%.

    Interaction Between Ultrafine Nano-Pd and Poly(vinylpyrrolidone)
    WANG Yan-Li*, TAN De-Xin, XU Guo-Cai, ZHANG Ming-Xu, ZHANG Hong-Yan
    2010, 31(5):  881-884. 
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    Ultrafine nano-Pd particles were prepared by ultrasonic without gas protection and reductant in the palladium(Ⅱ) chloride aqueous solution by the addition of a small quantity of poly(vinylpyrrolidone)(PVP); The samples were characterized by high-resolution transmission electron microscopy(HRTEM), Fourier transform infrared(FTIR) spectroscopy, ultraviolet-visible(UV-Vis) spectroscopy and X-ray photoelectron spectrum(XPS). The nano-Pd particles with a uniform size of a diameter of 3 nm were observed by HRTEM. FTIR analysis shows that the characteristic peak of carbonyl in the nano-Pd/PVP composites shifted 9 cm-1 to a lower frequency in comparison with that of the PVP. The results of UV-Vis spectroscopy show that the absorption peak of PVP shifted 16 nm to short wavelength after 50 min ultrasonic. Therefore, there are interactions between Pd and PVP. Based on the proving by XPS, the interactions were formed between the carbonyl group in the composites and the palladium atoms, and were considered to be of coordination and enabled nano-palladium particles to be dispersed stably.

    Aggregation of Urine Crystallites to Accelerate Formation of Urolithiasis
    LIU Yi-Ming, HE Jie-Yu, KUANG Li, WANG Feng-Xin, XIE Yu-Shan, OUYANG Jian-Ming
    2010, 31(5):  885-891. 
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    The variation of particle size, size distribution, aggregation state, intensity-autocorrelation function and ξ potential of the nanocrystallites in urine of lithogenic patients and healthy subjects following the placement time were comparatively investigated by nanoparticle size analyzer and transmission electron microscopy(TEM). As the placement period increased from 0 h to 3 h, the average diameter(Da) increased from 506 nm to 958 nm. The size distribution of particles became much wider, the autocorrelation time increased from 1.84 s to 3.93 s, and the ξ potential was decreased from -1.34 mV to -3.89 mV. However, Da in healthy urine increased only from 330 nm to 416 nm, the autocorrelation time increased from 1.44 s to 2.10 s, and the ξ potential was decreased from -8.35 mV to -8.90 mV. When the above process was repeated after these two types of urine samples received the second ultrasound treatment, all properties of urinary nanocrystallites basically repeated the above variation rules. It indicated that the nanocrystallites in the urine of lithogenic patients not only was distinctly different from those of healthy patients in particle size, size distribution, aggregation state, intensity-autocorrelation function and ξ potential, etc., but also had lower stability; the nanocrystallites in lithogenic urine can gradually agglomerate with the prolongation of placement period. These results are explained from the concentration difference between inhibitors with large and small molecules in the two types of urine, the stability of electric double layer formed on the surface of urinary nanocrystallites, etc. The results show that the aggregation of urinary nanocrystallites is the key factor to stone placement.

    Characterization and Tissue Pharmacokinetics in Mice of Arsenic Trioxide Magnetic Nanoparticles
    YANG Guo-Fu, LI Xiang-Hui, ZHAO Zhe, LIU Jia-Kun, WANG Wen-Bo*
    2010, 31(5):  892-895. 
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    In this study, As2O3-MgFe2O4 magnetic nanoparticles(As2O3-MNPs) were prepared by solvent-displacement method, and their characterization were studied by energy spectrum analysis, IR spectrum analysis and differential scanning calorimetry method(DSC). To guide the external magnetic field in the liver, the tissue pharmacokinetics of As2O3 in mice were also studied. The IR spectrum analysis indicats that there was MgFe2O4 in the As2O3-MNPs. The DSC results show that there was no interaction among As2O3, polylactic-glycolic acid(PLGA) and ferrite. The energy spectrum analysis indicates that MgFe2O4 and As2O3 were not adsorbed on the surface of MNPs but encapsulated in them. The As2O3 MNPs showed good magnetic targeting properties at pharmacokinetics in vivo. The liver tissue concentration-time area under the curve(AUC), peak concentration(cmax), the elimination half-time(t1/2) of the As2O3-MNPs in magnetic group were significantly greater than those in the other group respectively(all P<0.05). So the magnetic targeting effect of As2O3-MNPs was good. As a result, the As2O3-MNPs are promising in chemotherapy of tumor owing to their good stability and magnetic response propertie.

    Construction Mechanism of Nanometer Pyronine G Core-Ferritin Revealed with Circular Dichroism and Fluorometry
    CHEN Ying-Ying, HUANG Lin, JI Xue-Tao, LIN Qing, CHEN Ping, KE Cai-Huan, ...
    2010, 31(5):  896-904. 
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    Liver ferritin of Sphyrna zygaena(SZLF) with electrophoresis purity was prepared in bath to study its structure and function in batch. Under the condition of pH=2.0—10.0, circular dichroism and fluorometry were used to study the primary structural characteristics and change trend of secondary structure conversion both SZLF and apoSZLF, respectively, and revealed the stability, the interaction intensity, and the unfold behavior among subunits of SZLF shell. Using the approach of acidic and basic neutralization, the subunits of protein shell in SZLF can be disassociated, and these subunits disassociated can be also recombined into another new complete ferritin again, which sets up a reasonable technology for constructing a nanometer pyronine G core-ferritin(NPGCF). Both UV-Vis spectrophotometry and fluorometry were used to study the construction pathways of NPGCF, giving quantificationally twelve pyronine G molecules that were directly trapped into its protein shell for constructing NPGCF by each apoSZLF molecule. In addition, these techniques not only analyze both the pathway and the rate for trapping and releasing pyronine G, but also construct another new drug carrier of nanometer cisplatin core with high carrying capacity-ferritin.

    Interaction of S-Metolachlor with Calf Thymus DNA
    TONG Chang-Lun*, YE Rong-Min, ZHANG Quan, LIU Wei-Ping
    2010, 31(5):  905-910. 
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    The interaction of S-metolachlor with calf thymus DNA(ctDNA) was investigated using UV absorption spectra, fluorescence spectra, thermal denaturation and viscometry of DNA. The experimental results from UV absorption spectra show that when S-metolachlor was added, the red shift and hypochromic effect were observed in the absorption peak of ctDNA at 200 nm, while its effect on the absorption peak at 260 nm was very little, which indicate that the intercalation binding could be excluded. Moreover, the experimental results of the thermal denaturation and viscometry of ctDNA also excluded the possibility of the intercalation binding between the S-metolachlor and ctDNA. The fluorescence spectra indicate the intrinsic fluorescence of S-metolachlor could be strongly quenched by ctDNA, and with the temperature increasing, its quenching effect decreased, which suggest that the adducts of S-metolachlor and ctDNA were formed, and the binding constants were calculated. In addition, it was suggested from the results of the effect of the ion strength on the fluorescence system of the S-metolachlor-ctDNA that the electrostatic binding was also excluded. So, the possible binding mode between S-metolachlor and ctDNA was the groove binding according to the above experimental results.

    Interaction of Psoralen or Isopsoralen with Human Immunoglobulin
    HE Wen-Ying*, YAO Xiao-Jun, HU Zhi-De, CHEN Guang-Ying
    2010, 31(5):  911-918. 
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    The active components of plant herbs possessed analogical isomeride structure(psoralen and isopsoralen) were selected as research targets. A combination of intrinsic fluorescence, UV-Vis spectroscopy, FTIR and the molecular modeling technique has been used to characterize the binding between both coumarins and human gammagobulin(HG). The results from fluorescence spectroscopy indicated that the two drugs could interact with the protein strongly(binding constants between 0.251×104—3.503×104). The two drugs indicated the same static quenching mechanism for HG. The binding parameters for the different drug-protein systems are different under different temperatures(298, 308 and 318 K), and the binding modes were also different. The values of r are lower than 7 nm after interaction between the protein tryptophan residue and the bound psoralen or isopsoralen molecules(3.65 and 4.21 nm, respectively), which indicated the efficiency of energy transfer according to Förster theory. The secondary structure compositions of the globulin and the drugs complexs were estimated by qualitative and quantitative analysis from synchronous fluorescence spectra and FTIR experimental data.The molecular model studies revealed the analogial binding locations and identical binding mode for drug-HG systems. The similarities and differences between the results of these experiments may be related to the two isomers of the structure of psoralen and isopsoralen.

    Sorption Characteristic of Organochlorine Pesticides onto the Lighter and Heavier Components of Biofilms, Suspended Particles and Surface Sediments in Natural Water
    GUO Zhi-Yong, HUA Xiu-Yi, LIANG Da-Peng, DONG De-Ming*, LI Ming, LI Ya-Ting, SON
    2010, 31(5):  919-926. 
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    Lighter and heavier components of biofilms, suspended particles and surface sediments in natural water were separated by cesium chloride solution with a specific gravity of 1.8. The sorption of HCHs and DDTs on the solid materials and their lighter and heavier components was investigated through a batch-equilibration method. Sorption mechanisms were analyzed by comparing the contribution of these separated components. The results indicate that HCHs and DDTs partition in the mineral surface and amorphous organic matter is the main sorption mechanism of surface sediments. The linear partition mechanism and nonlinear pore-filling mechanism were simultaneously taken place in HCHs and DDTs sorption on Biofims and suspended particles due to their great heterogeneity and containing more complex components and structures.

    Metabonomic Study of Aristolochic Acid I-induced Acute Renal Toxicity Urine at Female and Male C57BL/6J Mice Based on 1H NMR
    LIU Xia, XIAO Ying, GAO Hong-Chang*, REN Jin*, LIN Dong-Hai*
    2010, 31(5):  927-932. 
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    The present work illustrates the metabolic changes of aristolochic acid I-induced acute renal toxicity urine at male and female C57BL/6J mice, which would help to understand the mechanism of renal toxicity and the differences in the metabolism at female and male mice after AAI treatment. The results showed that AAI nephrotoxicity mainly resulted from AAI inhibited the tricaboxylic acid cycle and energy metabolism,damaged the ecology of intestinal flora, changed the osmotic pressure inside and outside the kidney cells, depressed creatinine clearance rate and caused the injury of renal tubular and glomerular. Metabolic pattern analysis also showed that male mice were more sensitive to AAI renal toxicity than the female. These results suggested that urine 1H NMR-based metabonomics probably provides a novel insight into the study of drug toxicity mechanism and the toxicity gender differences.

    Construction, Photophysical and Electrochemical Studies on Ferrocene-phthalocyanine-fullerene Supramolecular Triads
    ZHAO Hai-Ying, CHEN Chen, ZHU Yi-Zhou, ZHENG Jian-Yu*
    2010, 31(5):  933-937. 
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    Much attention has been paid recently to the studies on photoinduced electron transfer in donor acceptor systems mainly to develop artificial photosynthetic systems and molecular optoelectronic devices. Several covalent and supramolecular phthalocyanine-fullerene systems have been prepared for this purpose, but only a few triads have been reported to date. In this article, ferrocene-phthalocyanine-fullerene supramolecular triads were constructed with pyridine- or imidazole-appended fulleropyrrolidine and covalently linked zinc phthalocyanine-ferrocene dyad via axial coordination. The stablilities of the triads(Kassoc=8.58×104 L/mol) were studied by optical absorption methods. Steady-state and time-resolved fluorescence measurements suggested that the occurrence of efficient photoinduced electron transfer(kCS =109 s-1) from excited phthalocyanine to fullerene entity in the triads with high charge-separation quantum yields(ФCS =0.88). The redox potentials were determined by cyclic voltammetric, and the driving forces(ΔGCS =-0.60 eV) were estimated to be exothermic, which favored the forming of charge-separation state.

    Structure-activity Relationship Studies on Inhibitors of Dihydroorotate Dehydrogenase Based on Pharmacophore Model
    BAO Hong-Juan, TANG Ya-Lin*, XU Xiao-Jie*, XIANG Jun-Feng, ZHENG Zhi-Hui, ...
    2010, 31(5):  938-946. 
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    The pharmacophore model of dihydroorotate dehydrogenase inhibitors was established guide the investigation on virtual screening for new dihydroorotate dehydrogenase inhibitors. Based on the training set composed of 31 DHODH inhibitors, pharmacophore models were generated by HypoGen program of the Catalyst software. The IC50 of the inhibitors varied from 7 to 63000 nmol/L. The pharmacophore models were a set of 3D pharmacophore features, which were constructed by the generation of conformational models and alignments of conformations based on the training set. The best model was validated to be highly predictive by two methods, namely, test set prediction and CatScramble method. This model consisted of two hydrogen-bond acceptors, and two hydrophobic regions. These features in the three-dimensional arrangement in the pharmacophore model could be characterized as hydrogen bond interaction, hydrophobic interaction and π-π interaction between ligand and acceptor. These features play an important role in determining the activities of bioactive molecules. The model′s correlation coefficient between the estimated and true activities for compounds constituting the training set were 0.8405, and for compounds from microbial metabolites were 0.8788. Using the pharmacophore model of DHODH inhibitors, 59 compounds with good estimated activities were found from microbial metabolites. New DHODH inhibitors may be found from these candidate compounds.

    Total Synthesis of the Dilignan threo-(±)-Diferuloysecoisolariciresinol
    XIA Ya-Mu, WANG Wei, YANG Feng-Ke*, CHANG Liang
    2010, 31(5):  947-952. 
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    Threo-(±)-diferuloysecoisolariciresinol which belongs to dilignans, has been firstly isolated from the trunk of Machilus thunbergii and exhibits a strong bioactivity. A novel synthetic route to threo-(±)-diferuloysecoisolariciresinol using Vanillina as the starting materials was described. The method involved two Stobbe reactions to construct the skeleton of lignan(C6—C4—C6), followed by LiAlH4 reduction, hydrogenation to form meso- and threo-(±)-secoisolanciresinol. threo-(±)-Secoisolanciresinol confirmed by NMR, IR and HRMS was the synthetic key intermediate, and then condensated with ferulaic acid to give threo-(±)-diferuloysecoisolariciresinol. The synthesis was based on a unified synthetic strategy to obtain target products through 11 steps, with yield of 8%. The synthetic method has the advantages of easy availability of starting materials, simple operation. So it has considerable practical value.

    Researches on the Mechanism of Single Strand Break Following the Alkylation of DNA Base Induced by Chloroethylnitrosoureas
    LIU Ting-Ting, ZHAO Li-Jiao*, ZHONG Ru-Gang
    2010, 31(5):  957-963. 
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    Density functional theory(DFT) and Mller-Pleset perturbation(MP) theory methods were carried out to investigate the mechanism of single strand break following the alkylation of DNA base induced by chloroethylnitrosoureas(CENUs). A multiple-step process, involving the decomposition of CENUs, the alkylation on DNA base, the hydrolysis of N—glycosidic bond, the ring-opening reaction of basic sites and the elimination of phosphodiester finally leading to the DNA strand break, has been examined. The geometries of stationary points(reactions, intermediates, transition states and product) were optimized at B3LYP/6-31++G** level. For simulating the reaction in cellular environment, the optimization or single energy computations were performed with the conductor-like polarizable continuum model(CPCM) model in water. The potential energy curve of the whole reactions was ploted by B3LYP/6-31++G** and MP2/6-311++G** computation respectively, then the results showed that the energy barrier of phosphodiester elimination reaction was the maximal value in the processes, while that of the alkylation reaction was the minimum. So a conclusion from theoretical analysis, which was consisted with the kinetics experimental phenomenon, was drawed that the alkylation reaction would be completed as soon as CENUs decomposed, and then the alkylated base would eliminate from the strand in a short time, however, the final DNA single strand break reaction would be a much more time-consuming process after the generation of the abasic sites.

    Modified Citrus Pectin: Preparation, Characterization and Anti-cancer Activities
    ZHANG Wen-Bo*, LIU Chang-Zhong, GAO Lin
    2010, 31(5):  964-969. 
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    Agarose gel electrophoresis, specific rotatory, HPSEC-RID, IR, 1H NMR, 13C NMR, periodate oxidation, GC-MS and methylation analysis were applied to investigate the homogeneity, chemical properties and structural features of modified citrus pectin(MCP). Results demonstrated that MCP was a homogeneous polysaccharide. Its molecular weight ranged from 21000 to 66000; the content of galacturonic acid was 81.0% and the degree of esterification was 2.13%. MCP contains Gal, Xyl, Rha and Ara; their molar ratio was 1.0∶1.5∶1.4∶1.3. Methylation analysis results confirmed that MCP had neutral sugar residues composed of Xyl, Ara and terminal Gal. Heptoma H22 was significantly inhibited by MCP and the inhibitor rate was 47.8%(n=10, p<0.01) at high-dose level(4 mg/kg). MCP also demonstrated anti-cervical carcinoma activity in U14 mice model. No anti-cancer activity was observed in Sarcoma 180 group.

    Synthesis and Biological Activities of 1-Acetyl-5-substituted Indoline Compounds
    CHEN Guo-Hua*, LUO Xiao-Chuan, ZHANG Jiang-Bo, HUANG Wen-Long
    2010, 31(5):  970-975. 
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    As benign prostate hyperplasia(BPH) is a common disease in elderly men, it is urgent to find new α1-adrenoceptor(AR) antagonists, the first choice for the therapy of BPH. On the basis of hybridization principle with 1-acetylindoline as the starting compound, two series of indoline derivatives 1-acetyl-5-{2-[4-(substituted phenoxy)ethyl]piperazin-1-yl}alkyl indoline and 1-acetyl-5-{2-[4-(substituted phenyl)piperazin-1-yl]alkyl} indoline were designed and synthesized. The structures of the target compounds were confirmed by 1H NMR, elemental analysis, IR and MS. Preliminary pharmacological test show all the target compounds exhibit certain antagonism of α1-AR. Compounds 9h and 12l perform better than piperazine, and are worth of further research.

    Synthesis and Properties of Novel Photochromic Dyads Based on Spirooxazine and Schiff Base
    YANG Su-Hua, PANG Mei-Li*, GUO Xin-Fu, LI Jing-Jing, HAN Jie, MENG Ji-Ben
    2010, 31(5):  976-981. 
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    A series of novel photochromic compounds(4a—4d) based on spirooxazine and Schiff base residue were synthesized. Their structures were characterized by 1H NMR, 13C NMR, IR, and HRMS. The compounds were proved by UV testing to have excellent photochromic properties both in organic solutions and polymer films. The compounds(4a—4d) have shorter photoresponsive time and better photosensitivity than parent compound 3. We have also studied the kinetics of the thermal decay process of the representative compound 4b in methanol, DMSO, and several kinds of films, and presumed why there are two kinds of explains about the kinetics of the thermal decay process in the recent years. The representative compound 4d shows a good fatigue resistance. The applications of compounds 4a—4d in photo-fluorescent and photo-magnetic switch area are under investigation.

    Preparation of Gd/Quantum Dots Multimodal Imaging Probes for Disease Diagnosis
    ZHANG Bing-Bo, GONG Xiao-Qun, LI Zhuo-Quan, GUO Fang-Fang, CAI Shao-Yu, ...
    2010, 31(5):  982-985. 
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    One of the major challenges in tumor research is early diagnosis in vivo. The current diagnostic methods, such as PET, MRI, and hematology tests, although effective in some aspects of tumor observations, are limited as a result of single functionality. Furthermore, the detection mechanism is often not compatible with the imaging system, making it difficult for accurate diagnosis. In this paper, MRI and fluorescence imaging were combined with several key contrast agents including quantum dots(QDs), gadolinium ion, silica, and poly(acrylic acid)(PAA) for high relaxation rate, strong fluorescent emission, and good biocompatibility, among which Gd/QDs were utilized for effective multimodal nano-probes. The experimental results from this study indicate a higher relaxation rate of the Gd/QDs multimodal nano-probes than that of silica-coated QDs without Gd. The t1-weighted MRI analysis show that these Gd/QDs based nano-probes can be potentially used for effective multimodal imaging agents.

    Coordination of Modified PAN Fibers with Fe3+ and Catalytic Activity of Their Complexes for Dye Degradation
    HAN Zhen-Bang, DONG Yong-Chun*, LIU Chun-Yan
    2010, 31(5):  986-993. 
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    The amidoximated PAN fiber(denoted as AO-PAN) and the mix-modified PAN fiber(denoted as M-PAN) were prepared with hydroxylamine and its mixture with hydrazine, and then used to coordinate with Fe3+, respectively, to produce two Fe-modified PAN fiber complexes(denoted as Fe-AO-PAN and Fe-M-PAN, respectively). Coordinating kinetics of both modified PAN fibers with Fe3+ was mainly studied, and effect of temperature and Fe3+ initial concentration on coordinating kinetics were also examined. The catalytic activities of both Fe-modified PAN fiber complexes were investigated in the oxidative degradation of an azo dye(Reactive Red 195) by DRS and ESR methods. The results indicated that within the observed temperature and concentration range, equilibrium data for the coordination of Fe3+ with two modified PAN fibers were obtained and correlated with Langmuir and Freundlich isotherm equations, and coordination kinetics showed better agreement with the Lagergren second order equation. Fe coordinating capacity and reaction rate constant of AO-PAN to Fe3+ were higher than those of M-PAN to Fe3+ at the same conditions, indicating that AO-PAN reacted with Fe3+ more easily than M-PAN. Two Fe-modified PAN fibers complexes have the significant catalytic effect on dye degradation, and Fe-AO-PAN showed the stronger catalytic performance than Fe-M-PAN in the dark. Moreover, catalytic ability of the Fe-modified PAN fiber complexes, especially Fe-AO-PAN was remarkably enhanced by light irradiation.

    Preparation of Pt-Pd/MWCNTs and Pd/MWCNTs Catalysts by Hydrothermal Synthesis in Room Temperature Ionic Liquids
    YANG Guo-Kai, DING Ke-Qiang*
    2010, 31(5):  994-997. 
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    The Pt-Pd/MWCNTs and Pd/MWCNTs were successfully prepared by a hydrothermal synthesis in which room temperature ionic liquid(RTILs) of EMIBF4 was used as solvents. XRD and EDS analysis strongly demonstrated the formation of Pt-Pd and Pd nanoparticles on the surface of MWCNTs. TEM images not only proved the preparation of Pt-Pd and Pd nanoparticles, but also illustrated that the average particle diameter of the obtained nanoparticles is close to 4 nm. CV and EIS tests showed in alkaline electrolyte, ethanol oxidation reaction(EOR) could proceed on the obtained catalysts modified GC electrode, also, except for the enhanced oxidation peak current, the potential onset of EOR was greatly negatively shifted for about 200 mV on the Pt-Pd/MWCNTs modified GC electrode compared with the case on the Pd/MWCNTs modified GC electrode.

    Effect of Gemini surfactant on the Interfacial Dilational Properties of Hydrophobically Modified Partly Hydrolyzed Polyacrylamide
    CAO Xu-Long*, ZHANG Lei, CHENG Jian-Bo
    2010, 31(5):  998-1002. 
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    The dilational viscoelastic properties of hydrophobically modified partly hydrolyzed polyacrylamide in the absence or presence of Gemini surfactant were investigated at the decane water interface by means of longitudinal method and the interfacial tension relaxation method. The dilational elasticity of polymer solution shows strong frequency dependence due to the fast process involving the exchange of hydrophobic micro-domains between the proximal region and distal region in the interface. Gemini surfactant plays different roles in influencing the structure of adsorbed polymer layer at different surfactant concentrations. At low surfactant concentration, the addition of surfactant molecules formed mixed film with polymer, resulting in the increase of dilational elasticity at low frequency. At the same time, polymer chain could sharply decrease the dilational elasticity of surfactant film mainly due to the weakening of the strong interactions among long alkyl chains in surfactant molecules. At high surfactant concentration, the addition of surfactant molecules can decrease the dilational elasticity of polymer solution due to the fast process involving in the exchange of surfactant molecules between the interface and the mixed complex formed by surfactant molecules and micro-domains.

    Selectivities of Elementary Reactions in 1-Hexene Pyrolysis
    ZHAO Ying-Xian*, YU Ying, CHEN Ming-Jie, WEI Feng
    2010, 31(5):  1003-1008. 
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    Pyrolysis of 1-hexene in temperature range of 873—973 K undergoes a chain mechanism of radical reactions. Primary products consist of C1—C3 paraffins, C2—C4 olefins, butadiene, cyclopentane, cyclopentene, coke and hydrogen. The formation of various products involve different elementary reactions with varying reaction path probability(RPP). Rising temperature promotes the homolysis of the feed molecule(chain initiation) and coke formation. The average reaction chain length(KCL) decreases from 5.86 to 5.19 with increasing temperature from 873 K to 973 K.

    2D-mapping Studies of the SERS Effect on the Single Ellipsoid Fe2O3@Au Particle
    SHEN Hong-Xia, WANG Mei, XU Min-Min, YAO Jian-Lin*, ZOU Wen-Jun, GU Ren-Ao
    2010, 31(5):  1009-1013. 
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    The single spindle Fe2O3@Au core/shell particle was employed as surface-enhanced Raman scattering(SERS) substrate and thiophenol(TP) was used as probe molecule to investigate the 2D-mapping and the distribution of SERS effect on the particle surface. The difference in the SERS effect from the tips and the middle part was compared. To obtaining the SERS effect from the different sites of the single particle, we firstly simulated with mathematic model and resolved the SERS 2D-mapping, the SERS effect from the edge of the particle was extracted. The results revealed that the difference in the intensity of SERS signal could reach 2—3 folders while the single core-shell particle was oriented at a certain angle relative to the polarization of excitation laser. Assumed the particle located in xy plane and the incident wave perpendicularly spread through z axis, the intensity of SERS signal exhibited the maximum value near the tip parts of the particle, while the other parts of the particle surface were very weak and the parts near the short axis were in minimum. By considering SERS mainly contributed by lightning rod effect of electromagnetism field enhancement, the local electric field enhancement of the spindle particles near the tip along long axis relative to short axis is about 5 times.

    FTIR Spectroscopy Study on Quantum Size Effect of CuOx Nanoparticles in CuOx/SiO2
    SU Wei-Guang, YING Pin-Liang, FENG Zhao-Chi, LI Can*
    2010, 31(5):  1014-1018. 
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    The nanosized CuOx/SiO2 catalysts were prepared by homogeneous deposition method with urea as the deposition reagent. The sizes of CuOx nanoparticles were adjusted by changing calcination temperatures of CuOx/SiO2 samples. The size and morphology of CuOx nanoparticles were characterized by TEM, and the adsorption behavior of CO on CuOx nanoparticles was also studied by FTIR spectroscopy. With increasing the sizes of the spherical CuOx nanoparticles from 3 nm to 11 nm, the intensities of IR bands of adsorbed CO on Cu+ ions are gradually decreased, and the frequencies of adsorbed CO are also red shifted from 2135 cm-1 to 2120 cm-1. It shows that the electronic properties of Cuδ+ are changed with increasing the sizes of CuOx nanoparticles, namely, the quantum size effect controls CO adsorption on CuOx nanoparticles.

    Relationship Between Photoluminescence Performance and SERS Effect of TiO2 Nanoparticles
    YANG Li-Bin, JIANG Xin, CHEN Lei, RUAN Wei-Dong, XU Wei-Qing, ZHAO Bing*
    2010, 31(5):  1019-1022. 
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    Pure and Zn-doped TiO2 nanoparticles were prepared by a sol-hydrothermal method and employed as surface-enhanced Raman scattering(SERS)-active substrates. The relationship between photoluminescence performance and SERS effect of TiO2 nanoparticles as well as photoluminescence mechanism were mainly investigated. The results indicate that surface properties of TiO2, such as surface defects and oxygen vacancies, etc, play important roles in the PL and SERS. When the contents of surface defects and oxygen vacancies are relatively low, the stronger is PL signal of TiO2 nanoparticles, the higher is SERS performance; however, when the contents of surface defects and oxygen vacancies are relatively high, the weaker is PL signal, the higher is SERS performance.

    Synthesis and Characterization of 9,9′-Diarylfluorene Hyperbranched Polymers
    JIN Jia, WU Yong-Gang*, BA Xin-Wu, BO Zhi-Shan*
    2010, 31(5):  1023-1028. 
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    Starting from 2,7-dibromofluorene, two aryl substituents were introduced to the 9-position of fluorene to replace the commonly used alkyl groups so as to increase the stability of fluorene. New hyperbranched polymers that exhibited excellent thermal and luminescent stability were synthesized using newly designed monomers through the “AB2+AB” approach. The decomposition temperatures of all hyperbranched polymers are above 400 ℃. The polymer films heated at 200 ℃ in air for 2 h were not observed green emission band. Compared with alkyl substituted polyfluorenes, the luminescence stability has a marked improvement. DSC results show that linear polymers have a glass transition at 170 ℃, but hyperbranched polymers do not have an obvious phase transition under 300 ℃, indicating hyperbranched polyfluorenes form amorphous films, which help to improve the efficiency of PLEDs.

    Theoretical Study of Electronic and Charge Transport Properties of Cruciform π-Conjugated 3,6-Diphenyl-1,2,4,5-(2′,2″-diphenyl)-benzobisazole
    DUAN Gui-Hua, WANG Li-Juan, ZHANG Hou-Yu*, GU Xin , Chen Jie, MA Yu-Guang*
    2010, 31(5):  1029-1033. 
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    The electronic and charge transport properties of a cruciform π-conjugated molecule 3,6-diphenyl-1,2,4,5-(2′,2″-diphenyl)-benzobisazole were investigated with density functional theory at B3LYP/6-31G(d) level. The molecular reorganization energy and charge transfer integral between the nearest neighbour molecule were calculated. The hole and electron mobilities are 0.31 and 0.11 cm2·V-1·s-1, respectively. Hole transport is mainly through the benzene "edge-to-face" interaction at terphenyl directions and displaced π-π stacking interaction of molecular center. While the main path for electron transport is the π-π stacking interaction in the benzobisazole direction. Mulliken charge analysis for the cationic and ionic state of molecule reveal that the hole and electron are mainly delocalized at terphenyl and benzobisazole directions, respectively. Such hole and electron transport at cruciform direction would be benefit for the balanced charge and electron transport, which might give the hints for practical applications in organic photoelectronic devices and design of novel charge transport materials.

    Quasi-Classical Trajectory Study of Stereodynamics for the O+HCl→OH+Cl Reaction
    XU Xue-Song, ZHANG Wen-Qin, DUAN Li-Hua, CHEN Mao-Du*
    2010, 31(5):  1034-1038. 
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    The stereodynamics of the O+HClOH+Cl chemical reaction were carried out with the quasi-classical trajectory method on Peterson ab initio potential energy surface. Four generalized polarization-depen-dent differential cross sections(2π/σ)(dσ00/dωt), (2π/σ)(dσ20/dωt), (2π/σ)(dσ22+/dωt) and (2π/σ)(dσ21-/dωt), the P(θr) distributions describing the k-j′ correlation and the dihedral angle distributions P(φr) describing the k-k′-j′ correlation are discussed under two collision energies 31.77 and 51.04 kJ/mol. The distribution of P(θr) shows that the degree of the rotational alignment of the product OH molecule is strong and sensitive to the collision energy. While the distribution of P(φr) indicates that the OH molecule is mainly aligned along y axis and insensitive to the collision energies in the CM frame.

    Function of the Hydrogen-bonding Network Between the Y-S-R Motif and the Heme Propionate Groups in sGC-HNOX Domain
    ZHANG Yue-Bin, CHENG Ying-Kun, Lü Ming, ZHANG Hua-Li, LI Zheng-Qiang*
    2010, 31(5):  1039-1044. 
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    Molecular dynamics methods were implemented to investigate the functions of hydrogen-bonding network between the conserved Y-S-R motif and the heme propionate groups in sGC-HNOX domain. The RMSD analysis reveals that the hydrogen-bonding network can stabilize the conformation of sGC-HNOX domain conspicuously during our simulation. The secondary structure, radius of gyration and solvent-accessible surface area of sGC-HNOX domain are not disturbed by the restraint hydrogen-bonding network. The principal component analysis on trajectory data and the heme configuration analysis indicate that the essential function of hydrogen-bonding network is to stabilize the binding of 4-E motif to 7-H motif, which is related to the structu-ral integrity of sGC-HNOX domain.

    Monte Carlo Simulation Study on Scaling Behavior in Growth of Antibody-antigen Complexes
    WANG Hai-Jun*, ZHANG Ping, BA Xin-Wu
    2010, 31(5):  1045-1050. 
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    The scaling behavior concerning the growth of antibody-antigen complexes was studied by the me-thod of Monte Carlo simulation. The validity of the algorithm we used is demonstrated by the excellent agreement between analytical results and those of Monte Carlo simulation under the case of equal reactivity. For both cases of equal and unequal reactivities, the scaling exponents of the size distribution, the weight-average binding degrees, and the characteristic correlation length are obtained, and then the scaling law on the sol-gel transition is checked. It is shown that the effects of unequal reactivity on the growth of antibody-antigen complexes are significant, and this can provide some useful information for the clinic analysis of immunoreactions.

    Phase Structure Study of Toughening Ethynyl-capped Polyimide
    WANG Da-Ming, DANG Guo-Dong, ZHAO Xiao-Gang, ZHOU Hong-Wei*, WANG Yun-Liang, ...
    2010, 31(5):  1051-1055. 
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    Thermosetting cross-linked polyimide(PI) prepolymer was synthesized from 4,4′-bisphenol A dianhydride(BPADA) and 3-aminophenylacetylene(APA) through a two-step polycondensation, modified by thermoplastic polyimides with different structures to form polymer blends. By regulating the quantity of thermoplastic polyimide, thermoplastic resins with similer structure and more flexible groups such as ether and symmetric methyl structures were introduced to the thermosetting/thermoplastic polyimide composite membranes. Differential scanning calorimeter(DSC) and scanning electron microscopy(SEM) were taken to evaluate the phase separation structure and compatibility of the system. The mechanical and thermal properties were also discussed. The results show that phase separation structure improve the mechanical properties of the mixture without sacrificing the excellent thermal stability of the original resin system.

    Synthesis of Poly γ-(2-thiazole-ureido)propyltriethoxysilane Metal Complexes and Its Magnetic Properties
    WU Lian-Bin, CHEN Qiu, BIAN Gao-Feng, CHEN Li-Min, SUN Wei-Lin*, SHEN Zhi-Quan
    2010, 31(5):  1056-1059. 
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    γ-(2-Thiazole-Ureido)propyltriethoxysilane(TUPTES) was firstly sythesized from 2-aminothiazole and γ-isocyanatopropyltriethoxysilane. The complexes PTUPTES-Cu and PTUPTES-Ni were prepared by sol-gel technology, respectively. Their properties were characterized by IR, 1H NMR, SEM and EDS. The magnetic behavior of the complexes were measured, which indicates that both of them were good soft ferromagnet at low temperature, the Curie-Weiss temperature is gained(T=119, 75 K), respectively.

    Effect of Chitosan Modification on the Behavior of the Immobilized Redox Enzyme on Nanofibrous Membranes
    HUANG Fu, WANG Zhen-Gang, WAN Ling-Shu, HUANG Xiao-Jun, XU Zhi-Kang*
    2010, 31(5):  1060-1064. 
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    Poly(acrylonitrile-co-acrylic acid)(PANCAA) nanofibrous membranes were fabricated by electrospinning process. The electrospinning of PANCAA was optimized and the nanofibrous membranes were characterized using field emission scanning electron microscopy(FESEM). Then, chitosan was tethered on the surfaces of the PANCAA nanofibrous membranes in the presence of EDC/NHS. The chemical changes of the membrane surface were characterized by attenuated total reflectance/Fourier transform infrared spectroscopy(ATR/FTIR) and water contact angle measurement. Catalase was immobilized onto the modified nanofibrous membranes using glutaraldehyde(GA) as coupling agent. The enzyme activity and stability were compared with those of the nascent nanofibrous membrane. The max activity was (1011.6±2.1) U/mg under 25 mg/mL chitosan and 2.5% glutaraldehyde for immobilized enzyme. It was found that the activity retention of the immobilized catalase was enhanced by 41.7% and the stability was also enhanced.