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Table of Content

    10 December 2008, Volume 29 Issue 12
    目次
    高等学校化学学报2008年第29卷第12期目次
    2008, 29(12):  0.  doi:
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    高等学校化学学报第29卷(1~12期)学科分类目次
    2008, 29(12):  0.  doi:
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    下期目次预览
    2008, 29(12):  0.  doi:
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    研究论文
    Application of Density Functional Theory to Molecular Magnetism——Theoretical Study on Magnetic Properties of Mixed-valence Trinuclear Manganese Compounds
    REN Jie1,2, WANG Bing-Wu1, CHEN Zhi-Da1*, XU Guang-Xian1
    2008, 29(12):  2331-2336.  doi:
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    On the basis of classifying mixed-valence compounds, the dimer coupling model was extended to trinuclear magnetic coupling systems. Particular emphasis is placed on the well-localized and well-delocalized mixed-valence compounds. As a representative example, the electronic structure for well-localized and well-delocalized [Mn3O(O2CH)6L3]z+(L=pyridine; z=0) model compounds were calculated via density functional theory, obtained the magnetic coupling constants J compared with experimental data. It is found that the density functional theory combined with broken symmetry approach can be applied to trinuclear mixed-valence systems considered. For well-delocalized mixed-valence Mn3Ⅱ,Ⅲ,Ⅲ system, the delocalization effect of the extra-electron on the magnetic coupling interaction must be considered, and thus the double exchange parameter B should be included in its Hamiltonian. For comparison the magnetic properties of the equivalence trinuclear [Mn3O(O2CH)6L3]z+(L=pyridine; z=1) were also calculated.
    Effects of GSH on the Activity of Two Glutathione Peroxidase Mimics
    ZHENG Qing-Chuan1, LÜ Shao-Wu2, ZHAO Yong-Shan1, MU Ying2, LUO Gui-Min2, SUN Chia-Chung1*
    2008, 29(12):  2337-2340.  doi:
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    6A,6A’-dianilino-6B,6B’-diselenide-bis-β-cyclodextrin(6-AnSeCD) was designed and synthesized to imitate the antioxidant enzyme glutathione peroxidase(GPX). The GPX activities of 6-AnSeCD and 6A,6A’-dicyclohexylamine-6B,6B’-diselenide-bis-β-cyclodextrin(6-CySeCD) were assessed in classical coupled reductase assay. 6-CySeCD exhibits better GPX activity than 6-AnSeCD in the reduction of H2O2 and cumenyl hydroperoxide by glutathione, respectively. And then, with the molecular dynamics(MD) simulations, the interaction between GPX mimics(6-CySeCD and 6-AnySeCD) and GSH were investigated. The MD results show great differences in the conformation and bond lengths between the each GPX mimics and the its substrate-enzyme complex, which demonstrate the possibility that such change might be the key factor for the bridge GPX mimics’ catalysis.
    Potential Energy Surface for Single-bond Breaking in Alkanes: Study from by Block Correlated Coupled Cluster Method with the CASSCF Reference Function
    SHEN Jun, FANG Tao, LI Shu-Hua*, JIANG Yuan-Sheng
    2008, 29(12):  2341-2344.  doi:
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    The block correlated coupled cluster(BCCC) method, with the complete active space self-consistent-field(CASSCF) reference function(CAS-BCCC in short), were applied to investigate the potential energy surfaces(PESs) for single bond breaking in hydrocarbons(methane and ethane). A comparison of our results with other theoretical estimates shows that the present approach can provide quantitative descriptions for the whole dissociation curve.
    Theoretical Study on Ions Selectivity of Calmodulin
    LÜ Yan-Yan, TAN Hong-Wei*, CHEN Guang-Ju, LIU Ruo-Zhuang*
    2008, 29(12):  2345-2349.  doi:
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    The structural and energetic characteristics of calmodulin binding Ca2+, Mg2+, K+ and Na+ were studied by molecular dynamics method. The detailed structure and energy of the four complexes were analyzed and discussed. The results reveal the structural difference between four complexes formed by calmodulin and metal ions. K+ and Na+ can departure from the calmodulin during the simulation, which prove that both ions could not coordinate to the EF-hand motif. Although Ca2+ and Mg2+ could coordinate with calmodulin effectively, large structural changes between the holo-calmodulin and the apo-calmodulin only are observed when Ca2+ bind to the EF-hand motifs. The energetic analysis suggest that the interaction between the Ca2+ and the EF-hand motif is much stronger than that of Mg2+, which brings the conclusion of this work that the interaction between ions and the calmodulin dictates the final structure of the complex and further activate the protein.
    Density Functional Study of the Structural and Electronic Properties of TiP10+/0/- Clusters
    TAN Kai*, LU Xin*, LIN Meng-Hai, ZHANG Qian-Er
    2008, 29(12):  2350-2353.  doi:
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    The geometric structures, stabilities of various isomers in TiP10 anion, neutral and cation were studied via density functional theory(DFT-B3LYP) method. At the levels of calculations employed, a sandwich structure is found to be the global minimum for neutral TiP10 cluster. The most stable TiP10+ and TiP10- clusters have sandwich structures similar to the neutral global minimum. Frontier molecular orbital(FMO) investigation suggests that the most important metal-ligand bond in sandwich structure is indeed a δ bond. The calculated vertical and adiabatic ionization potentials from the neutral global minimum(n-1) are 7.84 eV and 7.68 eV, respectively. The adiabatic and vertical electron affinity of the global minimum anion is predicted to be 3.35 eV and 3.18 eV.
    Theoretical Study on the Hydrolysis of N,N-Bis(p-fluorobenzyl)-N′-(2′,3′-dideoxy-3′-thiacytidinyl) Formamidine
    ZHANG Cheng-Hua1, XUE Ying1,2*, GUO Yong1, YAN Guo-Sen1
    2008, 29(12):  2354-2359.  doi:
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    Theoretical study on the hydrolysis mechanism of N,N-bis(p-fluorobenzyl)-N′-(2′,3′- dideoxy-3′-thiacytidinyl)formamidine(FBFA-3TC) was carried out at the B3LYP/6-31G(d,p) level. The solvent effect was evaluated using the conductor polarizable continuum model(CPCM) through the single point energy calculations at the B3LYP/6-31++G(d,p) level. Two reaction pathways are considered. Path A is the addition of water molecule to the C=N double bond in the amidine group in its first step and Path B is the attack of water molecule to the C-N single bond in its first step. The calculated results indicate that the first step in both pathways is the rate-limiting process and Path A is more favorable than Path B in the gas phase and in water. The solvent effects are not distinct. It is also found that the second step in Path A proceeds preferably according to Channel a, in which the second H atom of water transfers to the N atom in double bond of the amidine group, leading to products the modified cytidine and N,N-dibenzyl formamide.
    Density Functional Theory Study of NO+CO Reaction Mechanism on the Rh(111) Surface
    TIAN Kai1,2, TU Xue-Yan1*, DAI Shu-Shan1
    2008, 29(12):  2360-2364.  doi:
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    The NO+CO reaction mechanism on the Rh(111) surface were studied by the plane-wave density functional theory(DFT) with CASTEP program. The main elementary steps are taken into account, namely: NO dissociation,CO2 and N2 production, through the formation of the N2O intermediary species, and the classical N+N recombination.The transition states were confirmed for the main elementary steps by successful transition state search, and the activation energy were calculated, respectively.
    Theoretical Studies on the Reduction of N2O by CO on FeO+(6Σ+)
    WANG Yao, FU Gang, CHEN Ze-Ning, WAN Hui-Lin*
    2008, 29(12):  2365-2370.  doi:
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    The reduction of N2O by CO was investigated at the level of B3LYP/6-311+G(2d)//B3LYP/6-31G(d), using FeO+ as a model catalyst. The calculation results show that FeO+ is an effective catalyst which can pick up the O atom from N2O and then deliver it to CO to accomplish the overall O-transfer. Two species, Fe(O2)+ and OFeO+, were located during the reactions. While Fe(O2)+ is found to be more stable than OFeO+; the latter is shown to be more active than the former.
    Theoretical Studies on Shortest α-Helix
    JIANG Fan1,2, WU Yun-Dong1,2*
    2008, 29(12):  2371-2376.  doi:
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    We present the fully optimized structures of 4-residue and 5-residue α-helices at the B3LYP/6-31+G** level in solvent. The calculated backbone conformations are in good agreement with the statistical results from protein crystal structures. Similar to long regular α-helices, the fraying of the C-teriminal is observed. For short polyalanine peptide, 310-helix is significantly more stable than α-helix in enthalpy. However, the 310-helix is destabilized by entropy effect. In addition, it has been found that the capping effect by an aspartic acid at N2(second residue from the N-terminal) significantly stabilizes the α-helix over the 310-helix. Thus, the statistics that there are more shortest α-helices than 310-helices of the same length can be understood. It has been also found that the C-terminal of the shortest α-helix tends to end with a β-turn structure.
    DFT Studies on NLO Properties of Di-acridine Nitrogen-oxide Radical and Its Derivatives
    QIU Yong-Qing, DU Yan-Qing, LIU Xiao-Dong, SU Zhong-Min*, WANG Rong-Shun*, ZHAO Cheng-Da
    2008, 29(12):  2377-2380.  doi:
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    Seven radicals were designed according to di-acridine nitrogen-oxide radical which had been synthesized. Density functional theory(DFT) UB3LYP/6-31g(d,p) method was employed to calculate the stabi-lities and nonlinear optical(NLO) responses of these radicals in different spin states. The results show that the ground state of di-acridine nitrogen-oxide radicals and derivatives are stable in triplet state according with spin coupling rules. The polarizability αs and the second hyperpolarizability γs of radicals increase with donor and acceptor’s affiliation. Moreover, αs and γs increase obviously with increasing the ability to push/pull an electron. For first hyperpolarizability βtot, substituents have important influence on βtot in singlet state. The singlet radicals have the bigger NLO coefficients than the triplet radicals. Therefore, NLO property of system can be regulated by controlling spin multiplicity of system.
    Study of SN2-like Reactions in Terms of Molecular Face Theory
    YANG Zhong-Zhi1*, MIN Fang2, ZHAO Dong-Xia1, GONG Li-Dong1, DING Yan-Li1
    2008, 29(12):  2381-2388.  doi:
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    Using the molecular face theory, some features of the molecular faces at the stationary points of four SN2-like reactions and the Dpb values of some bonds along the IRC routes were calculated. Accordingly, using the Matlab software, the three-dimensional molecular faces, i.e., the electronic densities mapped on the molecular intrinsic characteristic contours, were depicted and analyzed. Then, the dynamic changing pictures of the molecular faces for the four SN2-like reactions are vividly shown.
    Molecular Dynamics Simulation of Adsorption of a Polyethylene Chain on Carbon Nanotube
    LIU Jia, ZHAO Li, L Zhong-Yuan, LI Ze-Sheng*
    2008, 29(12):  2389-2392.  doi:
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    The adsorption of a polyethylene(PE) chain on two kinds of carbon nanotubes(CNTs) was studied by classic molecular dynamics simulation. The diffusion coefficient and interaction energy of PE chain and CNT were calculated. The structure of the PE chain was analyzed by the dihedral distributing function and the order parameters. The results show that the PE chain is adsorbed firmly on the CNT, and the structure and the position of the PE chain mostly depend on the temperature and radius of the CNT.
    Theoretical Studies on Electronic Structures and Spectroscopic Properties of Cyclometalated Iridium(Ⅲ) Complexes
    WEI Zi-Zhang, WANG Gui-Chang, BU Xian-He*
    2008, 29(12):  2393-2397.  doi:
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    The ground- and excited-states geometries, electronic structures, absorptions and emissions of three iridium(Ⅲ) complexes, Ir(ppy)2(N^N)+ [ppy=2-phenylpyrine, N^N=bpy=2,2’-bipyridine(1); N^N=H2dcbpy=4.4’-dicarboxy-2,2’-bipyridine(2); N^N=Hcmbpy=4-carboxy-4’-methyl-2,2’-bipyridine(3)] were investigated theoretically. Their ground and excited state geometries were fully optimized at B3LYP/LANL2DZ and UB3LYP/LANL2DZ levels, respectively, and the calculated geometry of complex 3 is consistent with the X-ray results. At the Time dependent density functional theory(TD-DFT) level with PCM model, the absorption and phosphorescence properties of complexes 1—3 were calculated on the basis of the optimized ground and excited states geometries, respectively. The calculated lowest-lying absorption of complexes 1(384 nm), 2(433 nm) and 3(413 nm) are attributed to a MLCT/LLCT [dIr+π(ppy)→π*(N^N)] transition. The calculated phosphorescence of complexes 1(486 nm), 2(576 nm) and 3(567 nm) can be described as originated from a 3[dIr+π(ppy)]→[π*(N^N)] excited state with 3MLCT/3LLCT character. The calculated results show that the modulation of the lowest 3MLCT excited states can be achieved by grafting electron-withdrawing substituents on the coordinated ligands. In addition, nonlinear optical properties(NLO) calculations reveal that the static first hyperpolarizabilities(β0) are greatly enhanced through the introduction of the carboxy group into the bpy ligand.
    Theoretical Studies on Interaction Mode Between Human 2-Amino 3-Carboxymuconate 6-Semialdehyde Decarboxylase and Substrate and Inhibitor
    CHU Hui-Ying, ZHENG Qing-Chuan, ZHAO Yong-Shan, ZHANG Hong-Xing*
    2008, 29(12):  2398-2402.  doi:
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    The three dimensional structure of human 2-amino 3-carboxymuconate 6-semialdehyde Decarboxylase(hACMSD) was modeled and refined with homology modeling and molecular dynamics. And then, this model was assessed by Profile-3D and Procheck, which confirmed the refined model was reliable. The complex structures of the substrate or inhibitor with hACMSD were obtained and investigated through ligand-receptor docking studies by means of Affinity. The binding pattern predicted by the Affinity module reveals some important residues interacted with substrate or inhibitor, and provides a further refinement of the hACMSD/ inhibitor binding interaction as a basis for new structure-based design efforts.
    Density Functional Theory Studies on the Substitutional Site of Nitrogen in the Nitrogen-Incorporated ZSM-5 Zeolite
    WU Guang-Jun, WANG Xin, YU Ai-Min, WANG Gui-Chang, YANG Ya-Li, ZHANG Fu-Xiang, GUAN Nai-Jia*
    2008, 29(12):  2403-2406.  doi:
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    Density Functional Theory study was performed to predict the nitrogen substitutional site in the framework of nitrogen-incorporated ZSM-5 zeolite. All the calculations were performed on 8T clusters of ZSM-5 by Gaussian 98 program at B3LYP/6-31G, B3LYP/6-31G(d) and B3LYP/6-311G(d,p) levels, respectively. The calculations on energies of O atoms and N atoms show that the stability of N atoms in the framework has bigger effect on the reaction of substitution than the stability of O atoms. The O11 site, which is in the same tetrahedron with Brnsted acid, is the most preferred site for nitrogen substitution in the framework of ZSM-5 zeolite. So the Br nsted acidity on the surface of zeolite after nitridation is decreased.
    First-principle Theoretical Study of Structures and Properties of Finite-length Y-shaped Carbon Nanotubes
    XUE Bing-Chun, CAI Wen-Sheng, SHAO Xue-Guang*
    2008, 29(12):  2407-2412.  doi:
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    The geometry and electronic structure of finite-length(4,4) Y-shaped carbon nanotubes(CNTs) were investigated using density functional theory with GGA-PW91 method. The results indicate that the difference between the Y-shaped CNT and the pristine one is remarkable due to the influence of the defects in the junctions of the former. Furthermore, the structures and properties of Y-shaped CNTs are found to be rela-ted to the length of the CNT branch. By comparing the properties of the Y-shaped CNTs with different lengths, the length-dependent oscillation behavior including structure, energy gap and electronic property were observed when the length is longer than 1 nm.
    Theoretical Study of Structure and Stability of Fullerene Derivatives C50X(X=SiH2, PH, S)
    XU Xiu-Fang*, SHANG Zhen-Feng, LI Rui-Fang, ZHAO Xue-Zhuang*
    2008, 29(12):  2413-2419.  doi:
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    The structure and stability of all possible isomers of C50X(X=SiH2, PH, S) were investigated by ab initio HF/3-21G calculations. The calculation results indicate that the preferred position for cycloaddition of SiH2, PH, and S on C50 is consistent, i.e. on the C3—C4 and C4—C4 sites of C50, and the resultant most stable cycloaddition isomers are [5,6]-closed and [5,5]-closed structures. The main driving force governing the stability of the C50X(X=SiH2, PH, S) isomers is the strain, or the conjugative effect, or the combination of strain and conjugative effect, depending on the addition positions and the types of the attacked C—C bonds. Further, the structures and stabilities of C50X(X=SiH2, PH, S) are compared with those of the C50X(X=CH2, NH, O), and a general conclusion are drawn: the size of the attacking atom and the type of the attacked C—C bond are two decisive factors for the formation of open or closed structure of the C50X isomer.
    Computational Study of the Mechanisms for Methanol-assisted Ring-opening Polymerization of Lactide
    LIU Li, ZHU Rong-Xiu, ZHANG Dong-Ju, LIU Cheng-Bu*
    2008, 29(12):  2420-2424.  doi:
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    The stepwise addition/elimination and concerted mechanisms for the methanolysis of lactide, as a model for the initiation and propagation of ring-opening polymerization, were investigated computationally using B3LYP/6-31G(d,p) density functional theory calculations, with assistance from one, two and three methanol molecules. The results show that the extra methanol molecules acting as proton shuttles play a significant role in cyclic hydrogen-bonded clusters, and result in considerable energy savings. It is found that increasing the number of the ancillary methanol is accompanied by the reduction of the energy barrier for both stepwise and concerted mechanisms. The calculated results provide a general model that explains the mechanism of the titled reaction.
    Molecular Dynamics Simulation Using Graphics Processing Units
    SONG Guo-Liang, WENG Jing-Wei, LI Zhen-Hua, WANG Wen-Ning, FAN Kang-Nian*
    2008, 29(12):  2425-2429.  doi:
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    In this paper, the molecular dynamics program with CHARMM force field is developed on Graphics processing unit(GPU) at Windows computer cluster server(WCCS) system. From the testing results of peptide chain, the efficiency of GPU is outstanding compared with that of CPU. The efficiency on NVIDIA GeForce 8800 GT GPU is at lease 10 times faster than that on a single Athlon 20G CPU. When the total molecule size is enlarged, the number of vacant parallel units in GPU decreases, so the parallel efficiency increases. At the same time, while the fragment size is enlarged, the buffer size of a fragment decreases relatively, so the total efficiency also increases. The maximum efficiency ratio of GPU/CPU reaches to 28 times according to our test. At last, a peptide chain with 397 atoms is tested for simulation and the population of hydrogen bond is described at different time steps.
    DFT Studies on Unsaturated Ruthenium Carbonyls-heptacarbonyldiruthenium and Hexacarbonyldiruthenium
    LUO Qiong1, LI Qian-Shu1,2*
    2008, 29(12):  2430-2434.  doi:
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    Sixteen structures for Ru2(CO)n(n=7,6) were found by density functional theory(DFT) at the level of BP86/DZP++ and MPW1PW91/DZP++. The bond properties of these structures were discussed. Both the global minimum for Ru2(CO)7 and Ru2(CO)6 are doubly carbonyl bridged singlet structures. The dissociation energies suggest the preference for CO dissociation over rupture of the ruthenium-ruthenium bond in Ru2(CO)7. The potential applications in catalysis of carbonyl reaction are expected for these compounds.
    Effect of Polyene Chain Length on the Photophysical Properties in Diphenpolyenes
    PENG Qian1, NIU Ying-Li1, SHUAI Zhi-Gang1,2*
    2008, 29(12):  2435-2439.  doi:
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    By employing our nonradiative decay rate process coupled with time-dependent Density functional theory(DFT) calculations, we investigate theoretically the conjugation length effects on both the radiative and the non-radiative decay rates for diphenyl-polyenes. We find that the radiative transition rate constants hardly vary with the chain length because of the trade-off between the reduction of energy gap and the enhancement of oscillator strengths, but the non-radiative transition rate increases steadily indicating that the energy gap law governs.
    Theoretical Study of Reaction Mechanism of Ti, Na with O2
    ZHAO Li-Zhen, L Wen-Cai*, LI Xiao-Ping, QIN Wei
    2008, 29(12):  2440-2447.  doi:
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    The reaction mechanisms of Ti, Na with O2 were investigated at the MP2/6-311+G(d) level. Ti and Na atom were assumed to approach O2 in the manner of horizontally or vertically with respect to the O—O bond, respectively. Both neutral Ti/Na+O2 and anionic (Ti/Na+O2)- systems were considered. The binding energy and the charge curves for each reaction pathway were analyzed in detail, to validate the optimal reaction mode. The reaction of metal atom (Ti and Na) with O2 is easier in negatively charged system (Ti/Na+O2)- than the neutral Ti/Na+O2, and the vertical pathway is more favorable than the horizontal. Meanwhile, the calculated results show that Ti atom prefers to react with the singlet O2 in both neutral and negatively charged systems. Na is easy to react with the singlet O2 in the neutral system, but with triplet O2 in negatively charged system. The potential energy surface of Ti with O2 reaction was also calculated at CCSD(T)/6-311++G(3df)//MP2/6-311+G(d) for Ti+O2 and (Ti+O2)- systems.
    Theoretical Studies on Self-exchange Electron Transfer Between 2,3-Dicyano-5,6-dichloro-p-benzoquinone and Its Radical Anion
    QI Lin-Lin, WANG Quan-De, WANG Jing-Bo, FU Ke-Xiang, HE Fu-Cheng, LI Xiang-Yuan*
    2008, 29(12):  2448-2452.  doi:
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    We studied the self-exchange electron transfer reaction between 2,3-dichloro-5,6-dicyano-1,4-benzoquinone and its radical anion, on the basis of the non-equilibrium solvation theory in virtue of a constrained equilibrium state. Two different conformations of the parallel donor-acceptor complexes were considered. Using the new non-equilibrium solvation model combined with the linear reaction coordinate, we calculated the solvent reorganization energy in different solvents. The electronic coupling are obtained through the two-state model. The self-exchange electron transfer reaction rate constants in different solvents were calcu-lated and the results correlate well with the experimental values.
    Catalysis Mechanism Study on L1 β-Lactamase
    XU Ding-Guo*, YAN Guo-Sen
    2008, 29(12):  2453-2456.  doi:
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    The hydrolysis reaction of nitrocefin catalyzed by L1 β-Lactamase, which is a zinc containing enzyme was investigated, using combined quantum mechanics and molecular mechanics(QM/MM) and density functional theory. The research indicate that it is a two-step reaction: the first step is a nucleophilic attack reaction with cleavage of amide C—N bond, and the second one is the proton transfer process. We also investigated the role of zinc during the reaction.
    Theoretical Studies on NC3O Isomerization and Its Structures and Properties
    ZHAO Ying, SUN Chia-Chung, HUANG Xu-Ri*
    2008, 29(12):  2457-2461.  doi:
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    In this paper, DFT, QCISD and CCSD(T) quantum chemistry methods were used to investigate the isomerization of NC3O species. Five isomers were located including four chainlike species and one branched-chain species. They all possess considerable kinetic and thermodynamic stabilities. The results may provide a theoretical clue for the structures and properties related to interstellar molecules.
    Theoretical Studies on the Photochemical Reaction of Thioacetamide
    PENG Liang, DING Wan-Jian, YU Jian-Guo*, LIU Ruo-Zhuang*
    2008, 29(12):  2462-2468.  doi:
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    The B3LYP, MP2 and CASSCF calculations with cc-pVDZ and 6-31++G** basis sets were carried out to investigate the dehydrosulfide and C—C, C—N photodissociation reactions on their ground and the lowest triplet states. The effects that one water molecule from solvent directly takes part the dehydrosulfide reaction were studied carefully. It was concluded that none of these reactions was predicted to happen on the excited states. On the ground state, the proton transfer reaction is the main routine, while in the water or ethanol solution, the dehydrosulfide reaction can be predicted as the main reaction. We also use CASSCF method to optimize the stationary points and the conical intersection and intersystem cross points on the first excited states. Our calculations show that the chemical reactions except internal conversion on the S1 and T1 surfaces would not easy to happen. The possible mechanism could be that CH3CSNH2 was excited to S2 state T1, following a S2/S1 crossing. There are two paths to arrive the ground state from the first excited state: by a S1/S0 cross, or S1/T1 intersystem crossing to T1. It can be known based on our calculations that it is low possibility that CH3CSNH2 can process a photodissociation. This conclusion can help to consider thioamides in biology studies.
    Comparison Between [FeⅣ(O)(TMC)(NCMe)]2+ and [FeⅣ(O)(TMCS)]+ Non-heme Complexes of Geometric, Electronic Structures, Bonding and Reactivities
    WANG Yi, WANG Yong, HAN Ke-Li*
    2008, 29(12):  2469-2473.  doi:
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    Density functional theory(DFT) calculations were carried out to elucidate the electronic structures, Fe—O bondings and reactivities of six-coordinated [FeⅣ(O)(TMC)(NCMe)]2+ and [FeⅣ(O)(TMCS)]+ complexes. The geometric parameters calculated by a hybrid functional UB3LYP with LanL2DZ(Fe) and TZV(rest) basis set were in agreement with the experimental data. Analysis of the orbital coefficients and the bond orders showed that the TMC ligand does not have any equivalent orbitals that are affecting the Fe—O π bond. Due to the strong mixing of the iron 3d orbitals with the σ orbital of the thiolate ligand orbitals and a much less mixing with the acetonitrile as an axial ligand, the electronic properties of [FeⅣ(O)(TMC)(NCMe)]2+ and [FeⅣ(O)(TMCS)]+ are different and the Fe—O bond length of the [FeⅣ(O)(TMCS)]+ complex is longer than that of the [FeⅣ(O)(TMC)(NCMe)]2+ complex.
    Thermodynamics Theory for Sol-gel Transition of Branched Polymers
    WANG Hai-Jun1,3*, LIU Jin-Jun1,2, BA Xin-Wu1
    2008, 29(12):  2474-2478.  doi:
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    Several equilibrium properties of typical polycondensation system of Aa-Bb type were studied by the principle of statistical thermodynamics. Starting with the canonical partition functions constructed from two viewpoints, the explicit expressions of the equilibrium free energy and the law of mass action are obtained. Meanwhile, two new methods were proposed to derive the equilibrium size distribution, and the gelation condition was carried out by the isothermal compressibility. Furthermore, based on the invariant property of the equilibrium size distribution, the equilibrium free energies of sol and gel phases in postgel regime were given, and the relevant issues on the sol-gel phase transition were discussed.
    Analysis on the Thermodynamic Stability of Noble Metal and Valve Metal Elements in PEM-water Electrochemical Reactors by Applying the pH-potential-stability Diagrams Method
    CHA Chua-Sin*, HUANG Hong-Liang, WANG Qiang, LU Jun-Tao, ZHUANG Lin*
    2008, 29(12):  2479-2483.  doi:
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    Based on the analysis of distribution of interfacial potentials at various solid/PEM and solid/water interfaces within the PEM-water electrochemical reactors and well-known pH-potential diagrams, the construction of pH-potential-stability diagrams is suggested as a combination of these two methods to provide a clear-cut view of the stability problems of various materials in environments within various PEM-water electrochemical reactors. The pH-potential-stability diagrams of the noble metal and valve metal elements were constructed and employed in the analysis of the stability of these elements as electrocatalysts or construction materials in various PEM-water electrochemical reactors.
    Bubble Transfer Effect of Superhydrophobic Mesh Structure in Water
    WANG Jing-Ming1,2, ZHENG Yong-Mei3, JIANG Lei1*
    2008, 29(12):  2484-2488.  doi:
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    Gas/liquid separation is a fundamental process in many chemical or biological processes, especially for microfluidic systems, in which microchannel can impede or even stop liquid flowing. Recently, many researches are focused on bubble removal from where they form in order to avoid the above adverse effects occurring. However, the introduction of venting holes will cause the leakage of inner liquid. Superhydrophobic mesh structures can hold water droplets steadily, and its capability of leakage prevention is excellent for mesh with small size. Herein, microscaled and nanoscaled hierarchical structured copper mesh was fabricated by one-step solution-immersion process and it exhibited perfect superhydrophobicity. The component and morphology of the as-prepared sample were characterized by XPS, FTIR and ESEM. FTIR and XPS spectra demonstrate that the aggregates have a chemical composition of Cu[CH3(CH2)12COO]2. The ESEM images clearly show that clusters of continuous flowerlike architectures are formed on the copper mesh substrate. Then, bubble behavior on such special structures was investigated by high-speed camera. It is found that bubbles in water can easily vent out through the superhydrophobic copper mesh, while the case does not happen to hydrophilic copper mesh. These findings will provide a method in designing novel superhydrophobic materials in the near future, which may be developed into an effective degassing plate with bubble capture and distributed venting for microfluidic devices.
    研究快报
    Effect of Intramolecular Structural Environment on Bond Dissociation Energies
    QIU Yun-Feng, CAO Ze-Xing*
    2008, 29(12):  2489-2491.  doi:
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    The density functional calculations were used to explore the dissociation energies of [N(CH3)4]+ and [P(CH3)4]+ and their derivatives from substitution of H for CH3. The results show that the dissociation energies of C—N and C—P bonds gradually increase as the number of hydrogen atoms bonded to N or P increases in the derivatives, showing a remarkable effect of the intramolecular structural environment on the dissociation of the bonds. This dependence of bond dissociation energies on the local structural environment can be ascribed to the hyperconjugation interactions between the C—H bond and lone single electron of N or P. On the basis of NBO analyses, the bonding properties of dissociated fragments and their effects on dissociation energies were discussed.
    研究论文
    Morphology Control of AlPO4-5 Molecular Sieve in Mixed-solvents System Under Microwave Irradiation
    TIAN Da-Yong, LI Ji-Yang, YAN Wen-Fu, CAO Xue-Jing, YU Ji-Hong*, XU Ru-Ren
    2008, 29(12):  2492-2495.  doi:
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    The morphology control of AlPO4-5 crystals was achieved by microwave irradiation in mixed-solvents system. The results show that the aspect ratio of the AlPO4-5 (c/a) crystals decreases significantly with the increase of the volume ratio of EG to H2O. Interestingly, the dumbbell shaped AlPO4-5 crystals can be obtained when the volume ratio of n-butanol to H2O reaches to 5∶1 in the mixed-solvents of n-butanol and H2O. With the addition of the crystal seeds, the size of the AlPO4-5 crystals decreases with the increase of the amount of crystal seeds and the stirring time.
    Synthesis, Characterization and DNA-Binding Studies of Ruthenium Complex [Ru(bpy)2(PNT)]2+
    SUN Bin, LIANG Si-Min, WANG Yu-Chuan, CHAO Hui*, JI Liang-Nian*
    2008, 29(12):  2496-2501.  doi:
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    A novel ruthenium complex [Ru(bpy)2(PNT)]2+ (bpy=2,2’-bipyridine, PNT=2-[4’-(1H-tetrazol-5-yl)phenyl]-1H-imidazo[4,5-f][1,10]phenanthroline) was synthesized and characterized by elemental analysis, electrospray mass spectra and 1H NMR. The binding of the complexes with calf thymus DNA was investigated by absorption spectroscopy, luminescence titrations, viscosity measurements and DNA thermal denaturation experiments. The experimental results suggest that [Ru(bpy)2(PNT)]2+ binds with DNA by partial intercalation.
    Ionothermal Synthesis of Metal-organic Frameworks
    WANG Li-Feng, ZHU Guang-Shan, SHI Feng, FU Wei-Wei, JIN Zhao, QIU Shi-Lun*
    2008, 29(12):  2502-2505.  doi:
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    Two compounds, Zn3(BDC)3(MIA)2(1) and Zn(HBTC)(MIA)(BPY)(2)(BDC=terephthalic, MIA=N-methyl-imidazole, BTC=benzene-1,3,5-tricarboxylic, BPY=4,4’-bipyridine), were synthesized successfully in ionic liquids. X-ray diffraction analyses reveal that they crystallize in the monoclinic C2/c(1) and orthorhombic Fdd2(2) space group, respectively. Compound 1 exhibits a three-dimensional framework, and contains 0.9 nm×0.9 nm rhombic channels after the terminal coordinated N-methyl-imidazole removed. Compound 2 represents a supermolecule structure constructed through H bond and π…π interactions.
    Thin Film Preparation and Property of the Perovskite Manganites with Three Oxidation States
    HU Bin, YANG Ming, HOU Chang-Min, HU Shi-Qi, YUAN Hong-Ming, FENG Shou-Hua*
    2008, 29(12):  2506-2510.  doi:
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    Thin films of the perovskite manganese oxides with three oxidation states of Mn3+-Mn4+-Mn5+ were successfully prepared on the SrTiO3(001) substrates by off-axis radio frequency magnetron sputtering. The structure of the thin film is cubic with Pm3m space group, consisting of La3+, Ca2+ and K+ three kinds of ions occupied in A sites and three oxidation states of manganese in B sites, respectively. The as-made La1-x-yCaxKyMnO3 thin films are oriented multi-crystal epitaxial forms, as tested by the high energy(18 kW) X-ray diffraction and D8 discover X-ray diffraction with General Area Detector Diffraction System(GADDS). The AFM photographs show that the surface of the films is smoothy and the root-mean-square(RMS) increases along with the increase of the thickness. The results of the surface photovoltage(SPV) spectroscopy shows relatively strong signal, indicating the ability for the conversion of photoelectricity.
    Hydrothermal Synthesis of Silicon Oxide Nanowires in Solid-liquid Phase System
    MI Gang, CHEN Ping, REN Nan, ZHANG Ya-Hong, TANG Yi*
    2008, 29(12):  2511-2515.  doi:
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    In this paper, silicon oxide nanowires with P21212 space group were synthesized by liquid-solid phase hydrothermal method, using silica sol, Fe(NO3)3·9H2O and ethylenediamine-water solution as raw materials. Their structures were characterized by SEM, TEM, XRD and EDS. It was found that the reaction activity could be improved due to the employment of suitable silica and iron resources. As a result, the reaction conditions became more moderate, and less Fe species was used. An optimum experimental condition could be obtained, that is, the Si/Fe molar ratio of 1∶0.4, the ethylenediamine/water volume ratio of 8∶5, the temperature of 180 ℃ and the reaction time of 4 d. This approach is expected to provide a huge possibility for the industrialized manufacture of silicon oxide nanowires.
    Preparation of Hydrophobic Quantum Dots Using Oleylamine-hydrogen Selenide Complex as Precursor
    LIU Jian-Bo, YANG Xiao-Hai, WANG Ke-Min*, TAN Wei-Hong, LI Zhao-Hui, ZHANG Peng-Fei, WANG Dong
    2008, 29(12):  2516-2520.  doi:
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    A novel route was developed to synthesize hydrophobic quantum dots(QDs) using oleylamine-hydrogen selenide complex as the precursor. Fresh H2Se gas was introduced into oleylamine to form oleylamine-hydrogen selenide complex, and the complex was used as the precursor to prepare QDs by hot-injection solvothermal synthesis. The obtained QDs were characterized by photoluminescence spectroscopy, transmission electron microscopy and X-ray diffraction. The results show that the proposed method led to the formation of cubic CdSe QDs with narrow fluorescence full-width at half-maximum(25—40 nm), high photoluminescence quantum yield(up to 23%), and a broad emission spectra tunable from 480—610 nm. This is a low cost and environmentally benign technique for QDs preparation due to the absence of trialkylphosphine.
    Synthesis, Crystal Structure and Thermal Stability of 3D Heterometallic Bi(Ⅲ)-Pr(Ⅲ) Polymer Complex
    JIANG Qi-Ying1, DENG Hong-Quan1, ZHONG Guo-Qing1, HE Ping1, HU Ning-Hai2*
    2008, 29(12):  2521-2524.  doi:
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    A new 3D bismuth(Ⅲ)-praseodymium(Ⅲ) heterometallic complex, ({[(NO3)(H2O)3Pr(μ4-Hedta) Bi(NO3)2]·2H2O}2)n(edta=diaminetetraacecarboxylate), was synthesized and characterized by elemental analysis, FTIR, and X-ray diffraction single crystal structure analysis. It crystallizes in the monoclinic system, with space group P2(1)/n, a=1.26831(18) nm, b=0.82189(12) nm, c=2.3755(3)nm, β=105.055(2)°, V=2.3913(6) nm3, Z=4. Bridging Hedta3- anions between Bi atoms and Pr atoms result into a novel infinite 3D network structure. TG-DSC results indicate that thermal decomposition proceeds in several stages, dehydration, pyrolysis of ligand, and finally decomposition of salt.
    La3+ Induced Binding of Calmodulin(CaM) to CaM-binding Proteins in Rat Brain Homogenate
    XU Kun, YANG Xiao-Da*, WANG Kui
    2008, 29(12):  2525-2530.  doi:
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    Interactions of lanthanide ions with Ca2+/calmodulin(CaM) signal transduction is a crucial pathway for the biological effect of lanthanides. In the present work, the effect of La3+ on binding of CaM to its binding proteins(CaMBP) was investigated by an immobilized CaM affinity chromatographic method in rat’s brain homogenate. CaMBP binding to La3+-activated CaM gel were analyzed by SDS-PAGE and some CaMBP were identified by MALDI-TOF-MS. The concentration dependency on La3+ for CaM-CaMBP binding was determined in a mimetic cellular media and compared with that of Ca2+. The experimental results showed that (1) the CaMBP species activated by La3+ were primarily the same as those of Ca2+. Five selected CaMBP were identified to be 6-phosphofructokinase(PFK), glyceraldehyde-3-phosphate dehydrogenase(GAPDH)(enzymes in glycolysis), tubulin, actin(cytoskeleton proteins), and heat shock cognate 71000 protein(HSCP71, stress chaperone), indicating that La3+ may interfere with multiple cellular processes through CaM. (2) The effective concentrations for La3+ to induce binding of CaM to CaMBP depended on CaMBP species. Tubulin, actin and HSCP71 were observed to be sensitive to La3+ revealed by the affinity constants K of La3+ to CaM in the metal-CaM-CaMBP tertiary system, which are similar or higher than those of Ca2+. However, in the systems with PFK or GAPDH, La3+ bound to CaM less tightly. We hypothesized that this may attribute to complexity of mimetic cellular media and/or the effects of CaM-CaMBP interaction on CaM-metal binding, on which further studies should be appropriate. The work may offer new insight to the mechanisms of the biological effects of lanthanides.
    2-Amino-5-(p-dimethylamino)phenyl-1,3,4-thiadiazole as a Selective Fluorescent Chemosensor for Hg2+
    LIAO Qin-Xian1,2, LI Ai-Fang1, LI Zhao1, JIANG Yun-Bao1*
    2008, 29(12):  2531-2534.  doi:
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    A structurally simple 2-amino-5-(p-dimethylamino)phenyl-1,3,4-thiadiazole(1) was designed and synthesized as a high selective fluorescent chemosensor for Hg2+ in H2O/EtOH(volume ratio 1∶9) solution. The selective quenching by Hg2+ of the fluorescence of compound 1 was rationalized in terms of the formation of a nonfluorescent Hg2+-1 complex with enhanced intramolecular charge transfer compared to compound 1 itself. The 1∶1 binding mode of compound 1 with Hg2+by its S atom and N atom of C-2 NH2 was proposed on the basis of Job plots, IR, and 1H NMR titrations. A linear fluorescent response was found for Hg2+ over 5.0×10-6 to 5.0×10-5 mol/L with a detection limit of 1.0×10-7 mol/L.
    Cyclopalladated Ferrocenylimine Catalyzed ortho-Arylation of sp2 C—H Bond Substrates Containing the Directing Group
    LI Ya-Nan, YANG Fan, WU Yang-Jie*
    2008, 29(12):  2535-2541.  doi:
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    A novel and efficient catalytic system for ortho-arylation of sp2 C—H bond substrates containing the directing group using cyclopalladated ferrocenylimine as catalyst was developed. The arylation showed high regioselectivity and only occurred on the less sterically hinderd ortho-C—H bond. The reaction could be compatible to diverse functional groups such as CH3, CH3O, and CH3CO, as well as Br and Cl substituents, which would permit to be functionalized further to construct new compounds with more complicated structures.
    研究快报
    Fabrication of TiO2 @C Core-shell Nanofiber Arrays Electrode and Its Appdication in Electrochemical Sensing
    CHEN Rong-Sheng1, HU Liang-Sheng1, ZHANG Xu-Ming1, FU Ji-Jiang1, HUO Kai-Fu1,3*, CHU Paul-K.3, CHENG Jie-Ke2
    2008, 29(12):  2542-2544.  doi:
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    In this paper we describe a new method to fabricate TiO2@C core-shell nanofiber arrays for electrochemical sensing. The TiO2@C nanofiber arrays have been produced directly on titanium surface under acetone vapor at 800 ℃. This TiO2@C core-shell nanofiber arrays have the 40 nm TiO2 core in diameter and 5—10 nm carbon shell in thickness and show good electrochemical behaviors. The cyclic voltammogram in 1.0×10-3 mol/L K3Fe(CN)6 is quasi-reversible. The amperometric response increases linearly with the increase of the concentration of dopamine in the range of 1.0×10-7—1.0×10-4 mol/L. The detection limit(S/N=3) of dopamine is 2.45×10-8 mol/L.
    研究论文
    Colorimetric Chemosensing of Calixarene Derivative Possessing Bis(indolyl) Groups for Hg2+
    LI Zhe, GUO Dong-Sheng, LI Hong-Xia, LIU Yu*
    2008, 29(12):  2545-2548.  doi:
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    A calixarene derivative(2) possessing bis(indolyl) groups was synthesized in satisfied yield, and further its response to metal ions was investigated by the means of UV-Vis spectrometry. The results obtained show that host 2 displays a high sensitivity to Hg2+. The addition of Hg2+ made the absorption spectrum of host 2 appear a new band around ca. 500 nm, and caused obvious color change of solution from colorless to orange-yellow. Hence, the detection of Hg2+ can be easily found by naked eyes. Calixarene 2 may be used for the application as Hg2+-selective chemosensor, even in aqueous solution.
    Synthesis and Structure of p-tert-Butylthiacalixarene Derivatives Containing Benzothiazole Groups
    ZHAO Bang-Tun1*, DING Jing-Jing2, QU Gui-Rong2
    2008, 29(12):  2549-2553.  doi:
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    p-tert-Butylthiacalixarene(1) was alkylated with methyl iodide or dibromoalkane to obtain thiacalixarene intermediates 2 and 3 with the aid of potassium carbonate, respectively. A series of p-tert-butylthiacalixarene derivatives 5a—5d which append benzothiazol-2-ylthio groups at the lower rims were easily synthesized in good yields by the reaction of thiacalixarene intermediates 2 or 3 with 2-mercapto-benzothiazole in the presence of potassium carbonate. All the crystal novel compounds were characterized by 1H NMR, 13C NMR, IR, MS and elemental analysis. Meanwhile, the structure of thiacalixarene 5b was identified by X-ray diffraction analysis.
    Polymerization of n-Octylallene Catalyzed by Titanium Schiff-base Complex
    ZHU Wei-Wei, NI Xu-Feng*, SHEN Zhi-Quan*
    2008, 29(12):  2554-2557.  doi:
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    A titanium Schiff-base complex having two phenoxy-imine chelate ligands combined with Al(i-Bu)3 has high catalytic performance for the polymerization of n-octylallene. The complex [Ti(Salen)2Cl2] was synthesized with high yield by reacting the Schiff-base ligand with TiCl4 in n-hexane. The optimum reaction conditions for the polymerization are: n(M)/n(Ti)=100, n(Al)/n(Ti)=50, aged at 80 ℃ for 1 h, polymerized at 80 ℃ for 16 h in bulk, and the poly-n-octylallene obtained has 100% yield, Mw=1.1×105, MWD=1.77 and 50% 1,2-polymerized units.
    pH Stimulated Preparation of Polyrotaxane Based on Reversible Covalent Bond in Solution
    JIANG Yi1, XUE Jie1, ZHU Xin-Yuan1,2*, YAN De-Yue1*
    2008, 29(12):  2558-2562.  doi:
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    A novel method to prepare polyrotaxane in solution by α-cyclodextrins and dumbbell-like poly(ethylene glycol) derivative with reversible acylhydrazone bond and big end stopper (2’,4- dinitrophenyl) is described. Stimulated by the pH change to acidic in water at 60 ℃, the reversible acylhydrazone bond could undergo reversible hydrolysis. During this process, α-cyclodextrins can pass through the dynamic reversible bond and thread onto the polymer chain. Because of the relative strong supramolecular interactions between α-cyclodextrins and ethylene glycol units in water, more and more α-cyclodextrins thread onto the polymer chain, leading to the formation of polyrotaxane. Through the combination of 1H NMR, wide-angle X-ray diffraction, 13C CP/MAS NMR and differential scanning calorimetric tests, the formation of polyrotaxane prepared by dynamic method is confirmed. Differing from the traditional routes, the preparation of pseudo(poly)rotaxane is no longer a prerequisite to construct polyrotaxane in this dynamic method. The novel polyrotaxane with reversible covalent bond, which has its inherent dynamic property, has potential use in smart materials and self-healing materials.
    Preparation of Luminescent CdTe Nanocrystal-BaSO4 Composite Microspheres
    LIU Yi, ZHANG Hao, WANG Chun-Lei, YANG Bai*
    2008, 29(12):  2563-2568.  doi:
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    On the basis of the technique of surfactant bilayer modification, aqueous luminescent CdTe nanocrystals(NCs) were modified with DODAB layer and SDS layer. Due to the introduction of SO-4 sites on NC surface from SDS layer, NCs were further incorporated into BaSO4 composite microspheres through the stepwise addition of Ba2+ and SO2-4. The size and the composition of microspheres were characterized via SEM, TEM, confocal fluorescence microscope and XRD. Owning to the protection of BaSO4, the photoluminescence of as-prepared BaSO4-CdTe microspheres were more antacid than the original aqueous CdTe NCs.
    综合评述
    Some Progresses in Mechanistic Studies on Surface-Enhanced Raman Scattering
    DING Song-Yuan, WU De-Yin*, YANG Zhi-Lin, REN Bin, XU Xin, TIAN Zhong-Qun*
    2008, 29(12):  2569-2581.  doi:
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    In order to further develop surface-enhanced Raman spectroscopy to a versatile and ultra-sensitive diagnostic tool for surface, analytical, life and materials sciences, it is highly desirable to comprehensively reveal the mechanism of surface-enhanced Raman scattering(SERS). In this review article, emphasis is put on recent work of our group on the chemical enhancement(CE) mechanism. Three types of CE are classified as the enhancement by chemical-bonding, surface complex or photo-induced charge transfer. The electromagnetic(EM) field enhancement mechanism will then be introduced briefly, although it is to be considered the major contribution to SERS. Finally, a prospect of establishing the unified theory, that combines the CE and EM mechanism, will be discussed.
    Tuning Self-assembled Structures on Solid Surfaces by Exerting External Stimuli Investigated with STM and Progress
    ZHANG Xu1,2, WAN Li-Jun1*
    2008, 29(12):  2582-2590.  doi:
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    Controlling self-assembled adlayer on solid surface is a challenge in molecular science. Scanning tunneling microscopy(STM) is a powerful technique in the study of self-assembled structures. This paper summarizes recent STM study in tuning the structure of self-assembled adlayer by exert external stimuli such as solvent, heating, light irradiation, and electric field/electrode potential. The results will be significant in surface nanoscience and nanotechnology.
    Advances in Surface-enhanced Raman ScatteringSemiconductor Substrates
    ZHAO Bing*, XU Wei-Qing, RUAN Wei-Dong, HAN Xiao-Xia
    2008, 29(12):  2591-2596.  doi:
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    The advances of surface-enhanced Raman scattering(SERS) on semiconductor substrates, which is also the major research of our group in the past three years, are summarized in this paper. The application of semiductor nanoparticles explored the scope of SERS substrates. Some possible mechanisms different from noble metal substrates were discussed. The major contribution of semiconductor substrates for SERS maybe charge-transfer. Some phenomena, such as nanoparticle size dependence, half-width decrease of spectra, exciting line dependence, were discussed. The possible reasons of chemical enhancement, electromagnetic enhancement, surface defects of semiconductor, exciton Bohr radius were analysed.
    Advance in Lanthanide Complexes Based Electroluminescent Devices
    LI Zhe-Feng1,2, ZHANG Hong-Jie1*
    2008, 29(12):  2597-2608.  doi:
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    Lanthanide complexes are excellent luminescent materials with sharp emission bands and good color purity(FWHM<10 nm) as well as high inner-quantum efficiency(about 100%), which is helpful for fabricating bright, efficient and full-color OLEDs. So, the studies on lanthanide ion based electroluminescent devices are very important in application or theoretical researches. The researches on lanthanide ions based OLEDs mainly focus on Eu3+, Tb3+ ions, which have high emission efficiency; and Nd3+, Yb3+, Er3+ ions, which emissions are in the near infrared region. In this paper, mainly lanthanide ions based electroluminescent devices and their developments are reviewed. By dissertating EL properites of different Eu(Ⅲ) and Tb(Ⅲ) complexes, we find that luminescent properties of lanthanide ions are strongly depended on sensitization of ligands; Near-infrared lanthanide complexes(Yb3+, Nd3+, Er3+) have the potential applications in optical amplification, laser systems and biomedicine, etc..
    Probing Brain ChemistryMonitoring of Chemical Signal Molecules Release from Single-Cell, Single-Vesicle, Synaptic Cleft and Morphological Analysis with Nanoelectrochemistry
    CHENG Jie-Ke*, WANG Wei, WU Wen-Zhan, HUANG Wei-Hua*, WANG Zong-Li
    2008, 29(12):  2609-2617.  doi:
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    The monitoring of chemical signal molecules release from single cells with spatial and temporal resolution is a very important fundamental research in probing brain chemistry. In recent years, we have investigated systematically chemical signal molecules release from single cells with the microelectrode and developed the monitoring of chemical signal molecules release from single vesicles, single synapses and synaptic clefts with spatial resolution using the nanoelectrode. We have initiated the quantitative analysis to detect morphological changes of single cells before and after release using scanming electrochemical microscopy(SECM). We first researched the microfluidic and array-electrode integrated microsystem and applied it to the perfusion culture and detection of neurotransmitter release from cells. In this paper, the above researches and the frontier researches of this area in the world are reviewed. The new viewpoints of the future development in this research area are suggested. This review includes real time monitoring of dopamine release from single-cell using the microelectrode, monitoring of dopamine release from single vesicle with spatial and temporal resolution using the nanoelectrode, monitoring and manipulation of quantal release from single cells on a microfluidic device, morphological changes of single cells before and after NO release using the scanning electrochemical microscopy, and future analytical challenges: (1) research of decreasing the size of the nanoelectrode, (2) development of the integrated microfluidic device, (3) coupling between amperometry and other analytical techniques such as SECM, AFM, STM, TEM and (4) combination of Fluorescence Microscopy and Amperometry.
    Progress in the Studies of Cell Patterning
    BAI Hai-Jing, XU Jing-Juan, CHEN Hong-Yuan*
    2008, 29(12):  2618-2626.  doi:
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    As an effective experimental method, cell patterning is used for studying and controlling the beha-vior of cells and broadly involved with cell biology, tissue engineering, drug screening and wound healing, etc.. In the present paper, a series of fabrication approaches, the typical materials and smart substrates in cell patterning are reviewed with 100 references.
    Advance of Short Wavelength Near Infrared In-vivo Fluorescence Molecular Imaging
    MU Ying1, JIN Qin-Han1,2*
    2008, 29(12):  2627-2634.  doi:
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    Up to now, the diagnosis of cancers depends mainly on in vitro detection procedures and such imaging techniques as ultrasonic imaging, X-ray photography, X-ray computed tomography, nuclear magnetic resonance imaging and positron emission tomography(PET), etc.. The determination and confirmation of cancers are relying on the morphology and other macroscopic characteristics of tumor tissues or ill cells, and this is usually an invasive and time-consuming process. Such procedure is definitely not suitable for early diagnostics of cancers. Aforementioned imaging techniques are difficult to find the symptom of cancers at molecular lever. Thus, the early-stage diagnosis of cancers remains an unprecedented challenge that doctors are facing. Optical imaging technolgies, especially fluorescence molecular imaging(FMI), possess advantages of harmlessness, nonivasiveness, super sensitivity and possibility for in vivo multi-targeting imaging and are believed to have the possibility to realize the diagnosis of cancers at molecular and cell levels. In this review, several important advances of FMI techniques working in the short-wavelength near infrared region are introduced and critically reviewed.

    Probing Protein Functions via Optical Single Molecule Detection
    LI Xun, ZHAO Xin-Sheng*
    2008, 29(12):  2635-2642.  doi:
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    In the last two decades, optical single molecule detection(SMD) has been rapidly developed as a powerful tool in many research fields, especially, in biological systems. This mini-review focuses on the application of SMD in protein studies. Based on the unique advantage, namely providing detailed distribution of molecular properties and tracking individual molecules in real time, SMD is applied to not only equilibrium yet heterogeneous systems such as protein folding, enzyme reaction dynamics, and membrane dynamics, but also non-equilibrium events. SMD plays an essential role in tracking the motion of protein motors in vivo.
    Stacking Mode, Optoelectronic Property and Supramolecular Control
    Method in π\|Conjugated Organic Molecules
    YANG Bing, MA Yu-Guang*, SHEN Jia-Cong*
    2008, 29(12):  2643-2658.  doi:
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    Organic π\|conjugated molecules have been used in many kinds of optoelectronic devices, in which luminescence efficiency and carrier mobility are two key parameters to decide the optoelectronic device performance. Luminescence efficiency and carrier mobility of organic materials not only depend on the molecular structure, but also the stacking mode in aggregate state structure.In this paper, it is emphasized what is the relationship between the stacking mode of π\|conjugated molecules and their luminescence efficiency and carrier mobility in solid state, and how to adjust the stacking mode of π\|conjugated molecules, especially to realize the stacking mode we desire by the supramolecular interactions.The development of experiment and theory in relvent field is involved in detail.
    Facile Synthetic Strategy for Various
    Topological Polymers
    PAN Cai-Yuan*, YOU Ye-Zi
    2008, 29(12):  2659-2686.  doi:
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    With the advances of polymerization chemistry, especially controlled radical polymerizations, big progress on the synthesis of various topological polymers has been achieved. Different synthetic strategies have been deve-loped, among them, the heterofunctional initiator method is a facile and feasible approach, and has been extensively applied. This review describes the research progress on the application of this synthetic strategy in the preparation of various topological polymers, including block copolymers, miktoarm stars, H-shaped copolymers, π-shaped copolymers, graft polymers and cyclic polymers, but this review does not cover all published papers on this aspect. This synthetic strategy is based on the combination of different polymerizations, especially controlled polymerizations, and the combination of different controlled polymerizations with coupling reactions, such as “click” reactions, Diels-Alder reaction and active ester reaction etc.. The heterofunctional initiators discussed in this review include not only small organic molecules but also the polymers containing two or more initiation or chain transfer functional groups; the latter is also known as macro multifunctional initiators, which can initiate different polymerizations independently.