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Table of Content

    10 September 2011, Volume 32 Issue 9
    Contents
    Cover and Content of Chemical Journal of Chinese Universities Vol.32 No.9(2011)
    2011, 32(9):  0. 
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    Review
    Artificial Molecular Devices and Machines Based on 24-Crown-8 Macrocyclic Compound
    ZHANG Zhi-Jun, ZHANG Heng-Yi, LIU Yu*
    2011, 32(9):  1913-1927. 
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    A variety of artificial molecular devices and machines have been constructed based on supramolecular systems which including the rotaxanes, catenanes and pseudorotaxanes containing the 24-crown-8 ring and relative positive organic guests. The chemical and physical methods which can be used to operate the molecular devices and machines by controlling the input of 1)acid-base 2)competitive agents 4)anions 3)light 4)heat 5)red/ox potential 6)protecting group 7)solvents were discussed. The switchable strategy based on motion of threading/dethreading in pseudorotaxane can be used to perform a great deal of functions. In rotaxane and catenane systems, the function of molecular machines can be performed through varying the relative positions and orientations of the components to realize shuttling and circumrotation motions utilizing the inputting energy.
    Anions Mediated Foldamers
    WANG Ying, GAN Quan, JIANG Hua*
    2011, 32(9):  1928-1938. 
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    The aims of research in the field of foldamers are to design, synthesize and characterize artificial oligomers with a well-defined folded and compact structure similar but not identical to its natural counterparts such as proteins. Foldamers provide a simple and efficient approach for investigating molecular recognitions in particular anion recognitions. The focus of this review is on the recent advances regarding foldamers that self-assemble with the assistance of anions.
    Anion Binding, Recognition and Separation by Urea\|based Receptors
    WEI Mei-Ying, LI Shao-Guang, JIA Chuan-Dong, WU Biao*
    2011, 32(9):  1939-1949. 
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    Urea can be used as an important and effective unit to build up anion receptors because it’s ability of binding anions by donating two parallel H-bonds. It is convenient to detect interactions of receptors and anions for urea-functionalized anion receptors. This review highlights the developments about anion binding, recognition and separation of mono-, di-, poly-ureas and metal-assisted ureas receptors in recent years.
    Progress in Synthesis of Cycloaramides and Self-assembly Behavior
    YANG Yong-An, FENG Wen, YUAN Li-Hua*
    2011, 32(9):  1950-1961. 
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    In this review we summarize the recent progress in synthesis of cycloaramides assisted by three-center hydrogen bonding and the remote steric effect, and their self-assembly behaviors of these macrocycles. The strategies for preparing shape-persistent aromatic oligoamide macrocycles with different cavity sizes are discussed based on the highly efficient, one-step macrocyclization. The self-assembly properties of these cycles can be manipulated by means of altering side chains on the periphery. A brief account of cycloaramides with some applications is also given.
    Study on Nanometer Hybrid Low Dielectric Constant Materials from Polyhedral Oligosilsesquioixanes
    XU Hong-Yao*, YAN Zheng-Quan, ZHANG Chao, SU Xin-Yan, GUANG Shan-Yi
    2011, 32(9):  1962-1969. 
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    Polyhedral oligosilsesquioixanes (POSS) is a nanosized organic-inorganic hybrid molecule, which consists of a well-defined cage-like nano inorganic core [(SiO1.5)n] surrounded by organic corner groups. The unique structure of POSS molecules provide a an important platform for controllably preparation of hybrid nanocomposites in molecular level dispersion. In this paper, the influence of hybrid molecular structure on properties and forming mechanism of low dielectric constant, in particular, the research progress of POSS-based nanocomposite low dielectric constant materials were summarized.
    Recent Advances in Researches of Triazole-based Supramolecular Chemistry and Medicinal Drugs
    CHANG Juan-Juan, WANG Yan, ZHANG Hui-Zhen, ZHOU Cheng-He*, GENG Rong-Xia, JI Qing-Gang
    2011, 32(9):  1970-1985. 
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    Triazole ring contains three nitrogen atoms, is a quite important five-member heterocycle and possesses aromaticity and rich electrons. This unique structure endows triazole moiety to readily accept protons and coordinate with various metal ions. Therefore triazole compounds easily form supramolecular aggregates via non-covalent interaction such as coordination bonds, hydrogen bonds, ion-dipole, cation-?, ?-? stacking, hydrophobic effect, van der Waals force and so on. These triazole derivatives exhibit various special properties and biological activities, and display a wide range of potential application as artificial ion receptors, materials and medicinal agents. In recent years, the related researches of triazole-based supramolecular chemistry and medicinal drugs have been becoming an extremely active, quite rapidly developing and attracting highlight area. Combining with authors’ researches and referring other works from literatures in recent 5 years, this work for the first time systematically reviewed the recent advance of the whole range of triazole-based compounds as cation and anion receptors and triazole supermolecules as luminescent and magnetic materials as well as medicinal drugs majoring in antibacterial, antifungal, anticancer agents. Hopefully, this review would be helpful for the further researches and development of the triazole-based supramolecular chemistry and medicinal drugs.
    Recent Progress in Pyridinium\|based Anion Receptors
    BAO Shuang , GONG Wei-Tao* , NING Gui-Ling
    2011, 32(9):  1986-1995. 
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    This review summarizes the recent development of the pyridinium-based receptors in the field of anion recognition and sensing. It covers the main design principles, anion recognition abilities and mechanisms of the pyridinium-based receptors including acyclic, macrocyclic and interlocked systems.
    Application of Supramolecular Chemistry on Pharmaceutical Cocrystals
    CHEN Jia-Mei, WU Chuan-Bin, LU Tong-Bu*
    2011, 32(9):  1996-2009. 
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    Pharmaceutical cocrystal is a new type of pharmaceutical crystalline state. It is attractive to pharmaceutical scientists because it can provide a number of crystalline states for a given active pharmaceutical ingredient (API), in which the physical and chemical properties of the API can be adjusted by pharmaceutical cocrystal. In this review, we address pharmaceutical cocrystals from the perspective of supramolecular chemistry, and present a series of structures of pharmaceutical cocrystals constructed through hydrogen bonding supramolecular synthons, in which the physical and chemical properties (solubility, bioavailability, melting point etc.) of APIs can be changed by pharmaceutical cocrystal.
    Recent Progresses in Sugar\|functionalized Macrocyclic Compounds
    YANG Fen, ZHANG Xin-Jian, CHEN Qi, YAN Chao-Guo*, HAN Bao-Hang*
    2011, 32(9):  2010-2021. 
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    Carbohydrates, as a special substrate of specific receptors in many biological processes, play an important role in information communication. In recent years, more and more novel sugar-functionalized macrocyclic compounds such as calixarenes, cyclodextrins and crown ethers have been efficiently prepared and show the potential applications in lectin-pecific biological binding, selective ion recognition, and chiral catalysis. Introducing sugars into the macrocyclic system can not only produce various novel multivalent glycoconjugates, but also provide new binding sites for the macrocyclic compounds, which attracts more and more attention. In this review, recent progresses in the synthesis and applications of sugar-functionalized macrocyclic molecules have been summarized.
    Progress of Cucurbit[n]urils in Drug Delivery System
    HUANG Ying, TAO Zhu, XUE Sai-Feng, ZHU Qian-Jiang
    2011, 32(9):  2022-2031. 
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    As a type of novel synthetic acceptor, cucurbit[n]urils(Q[n]s) which has the unique structure with hydrophobic central cavity and hydrophilic carbonyl group portals, can selectively bind different guest molecules to form self-assembly host-guest complexes, capsules and supramolecular entities. Thus, cucurbit[n]uril could be used in many different fields, such as environment, pharmacology, separation and material. Combining with our researches and referring other works from literatures, this paper reviewed the recent advance of cucurbiturils in the drug carriers and drug delivery, and the prospect of the cucurbituril in pharmacology were also presented.
    Imidazolium and Pyridinium Based Receptors for Anion Recognition and Sensing
    DONG Zhi-Yun, JIANG Xiao-Zhi, XUE Yun-Rong, FENG Mei-Yun, GAO Guo-Hua*
    2011, 32(9):  2032-2045. 
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    The development of imidazolium and pyridinium based anion receptors is a very important field for the anion recognition. These kinds of anion receptors possess a great deal of merits such as various host structures, synergistic effects of hydrogen bonding, hydrophobic interaction, electrostatic interaction, π-π stacking , anion-π interaction and so on. The design, structure and anion recognition and sensing of imidazolium and pyridinium based receptors are reviewed.
    Recent Progress in Superoxide Dismutase Mimics
    LI Chen, YANG Zheng, SHE Meng-Yao, YIN Wen-Ting, LI Jian-Li*, ZHAO Gui-Fang, SHI Zhen
    2011, 32(9):  2046-2061. 
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    Superoxide dismutases are ubiquitous in living systems. These enzymes serve a vital role in defending oxygen-utilizing life forms from oxidative damage. The natural superoxide dismutases can catalyze the dismutation of the free radical superoxide and have efficacy in disease states, partly, mediated by superoxide, such as oxidative stress, cancer, and inflammation. The practical use of Superoxide dismutases in biological systems is problematic due to dif?culties associated with the systematic infection of protein. As a result, tremendous researches were made in this area in recent years on the rational design and synthesis of low molecular weight catalysts which mimic a natural SOD enzyme function. Low molecular weight mimics could have significant advantages over SOD enzymes such as lack of immunogenic response, longer half-life in the blood, improved access to cells and intercellular space, potential for oral delivery, and low costs. This review described the recent progress of superoxide dismutase mimics on the design, synthesis and application.
    Supramolecular Surface Modification of Carbon Nanomaterials and Their Applicaions
    CHENG Qian-Yi, ZHOU Ding, HAN Bao-Hang*
    2011, 32(9):  2062-2070. 
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    The carbon nanomaterials possess unique physical and chemical properties due to their special structure, and become one topic of high interests in recent years. The supramolecular surface modification could improve their surface properties and dispersion ability, which have attracted widespread attention from the scientific communities. The current status about the modification of carbon nanomaterials, especially carbon nanotube and graphene, through various intermolecular interactions, such as ??? interaction, hydrophobic interaction, hydrogen bonding, and electrostatic interaction, as well as their applications, such as in optoelectronic materials, drug and gene delivery systems, and chem- or biosensors were summarized and reviewed in this paper.
    Stabilities of Supramolecular Complex Structures in Lipid Rafts Microdomains
    SUN Run-Guang*, ZHANG Jing, HAO Chang-Chun, CHEN Ying-Ying, YANG Qian
    2011, 32(9):  2071-2086. 
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    The dynamic and stability characteristics of lipid raft in the biomembrane have great effect on many biological processes. Extracted lipid rafts from animal cells, not only flask-shaped caveolae but also spherical and ellipsoidal morphology have been observed. Simulated the lipid raft in vitro and focused on the binary and ternary system to study the polymorphisms of membrane structure. The results showed that SM/Chol bilayer appeared tightly clustered irregular microdomains with the increase in surface pressure. For the SM/Chol/DOPC bilayer system, the microdomains formed by SM/Chol floated on the fluid small DOPC area. When DOPE added to the SM/Chol, the bilayers structure became unstable. Ceramide induced SM/Chol bilayer rearrangement, from original irregular structure to closely aggregated round structure. In the mixed monolayers, the molecular area and surface Gibbs free energy determines the molecular interactions. When the excess molecular and excess Gibbs energy is negative deviations from ideality, the interaction between molecules is attractive and the monolayer is more aggregated. Positive deviation from linearity indicates repelling interaction and the monolayer forms phase separation structure. The less the Gibbs energy value, more stable the monolayer is. Combined extraction from animal cells and simulated in vitro methods, study the biological significance of lipid raft between structure and function from super-molecular level. This project conduction can provide theoretical evidence and experimental support for studying biomembrane.
    Preface
    Synthesis of 37-Crown-10 and Its Selective Binding Abilities with Cations
    CHEN Ling, ZHANG Heng-Yi, LIU Yu*
    2011, 32(9):  2087-2090. 
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    A new asymmetric 37-crown-10 (1) with a pyromellitic diimide unit and a 1,5-naphthalene unit was synthesized, and its structure was resolved by X-ray diffraction. The binding behaviors of 1 with some cations were investigated by UV and 1H NMR spectroscopies. The crystal structure obtained shows that there are two smaller cavities due to the strong interaction from the intramolecular charge transfer. The structural feature is beneficial to the complexation of 1 with smaller cations. The UV experiments show that its binding ability for lithium is the strongest, that for sodium is weak, and no binding for other akali metal or alkaline-earth metal ions.
    Design and Preparation of Fluorescent Bisimidazole\|Ag(Ⅰ) Coordination Polymeric Gel
    LUO Liang, LI Wei, GAO Ge, LAN Jing-Bo*, YOU Jing-Song*
    2011, 32(9):  2091-2096. 
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    A novel BODIPY functionalized imidazole derivative 5 has been designed and synthesized. Utilizing coordination of rigid bisimidazole moiety and photoluminescence properties of BODIPY, we have achieved formation of a fluorescent coordination polymeric gel, which has been characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM) and photoluminescence spectroscopy. The results show that the emission wavelength and fluorescence intensity of fluorophore were not affected by the adding Ag+ and photoluminescence properties of ligand 5 in the gel phase were retained. This result is another successful example of our research in rigid bisimidazole-Ag(I) coordination gel, which offers an opportunity for forging versatile fluorescent coordination polymeric gels.
    Construction of Unsymmetrical 1,4-Dihydropyridines via Integration of Hetero-source Self-sorting Domino Reactions
    GAO Meng, YANG Yan, WANG Zi-Hua, ZHANG Dong-Xue, WU Liu-Ming, DENG Cong, SHU Wen-Ming, WU An-Xin*
    2011, 32(9):  2097-2102. 
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    On the hypothesis that hetero-sources could involve in self-sorting domino reactions and generate suitably functionalized intermediates to converge on the final product, we present herein a simple model of this strategy for the preparation of unsymmetrical 1,4-dihydropyridines. In the presence of CH3COONH4 and 3-nitrobenzaldehyde, two different 1,3-dicarbonyl compounds, respectively, generate the enamine and enone intermediates, which could finally combine with each other to efficiently afford the unsymmetrical 1,4-dihydropyridines. Direct 1H NMR analysis of the reaction mixture further proved the high selectivity of this reaction, which indicated the high self-sorting behavior of different domino reactions and their final convergent property. We anticipate that these results should inspire the design of more efficient domino reactions for the preparation of complex products from simple materials via integration of hetero-source self-sorting domino strategy.
    Synthesis of Tetrathiafulvalene-calixarene Derivatives and Their  Intermolecular Electron Transfer Towards Tetrachloro-1,4-benzoquinone
    ZHAO Bang-Tun*, LIU Lian-Wei, DING Jing-Jing, QU Gui-Rong
    2011, 32(9):  2103-2108. 
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    Two ether-linked tetrathiafulvalene-calixarene derivatives were designed and synthesized,and their chemical structures were characterized by 1H-NMR, 13C-NMR, FAB Mass spectra and IR. Their electrochemical properties have been investigated using cyclic voltammetry method. And UV-Vis spectra was used to exploit the intermolecular electron transfer between the target compound (4a, 4b) and tetrachloro-1,4-benzoquinone (Q) regulated by metal ions (Na+, K+, Ba2+). The results the K+ may effectively promoted the electron transfer between 4b and Q system.
    Selective Colorimetric Recognition Properties of the Bis(indolyl)methene Receptors for Amino Acids
    WANG Li-Tao, HE Xiao-Ming, GUO Yong, XU Jian, SHAO Shi-Jun*
    2011, 32(9):  2109-2113. 
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    The development of artificial receptors for the selective recognition of biologically important species has been one of the best concerned topic in the field of supramolecular chemistry. However, compared to the large number of chromo/fluororeceptors for cations or anions, the development of artificial receptors for amino acids is quite limited. The effective and selective molecular recognition or sensing of unprotected amino acids in aqueous solution is still a challenging problem due to their highly hydrophilic character. In this paper, a series of 3,3′-bis(indolyl)methene receptors were designed and synthesized, and the recognition properties of the receptors for 20 natural amino acids have been studied using UV-Vis spectroscopic techniques. The result indicated that the receptors exhibited selective colorimetric sensing for amino acids by protonated/deprotonated process of the hydrogen bond site of the receptors in CH3CN/H2O (1:1, v/v). The introduction of methoxy group into indole ring, which increased the basicity of the hydrogen bond acceptor unit, can promote the occurrence of the protonated process and increase the sensing sensitivity for acidic amino acids. The receptors with nitro group exhibited obviously colorimetric sensing for basic amino acids (arginine, lysine) due to the deprotonation of the hydrogen bond donor unit of receptors. In CH3CN/H2O (1:1, v/v; 0.01 M HEPES, pH=7.4) neutral buffered solution, the receptors without nitro group showed negligible spectral responses for various amino acids, but the nitro-substituted receptors exhibited high selective colorimetric sensing for cysteine (Cys) and homocysteine (Hcy) based on the nucleophilic addition reaction between the sulphydryl group of Cys/Hcy and the meso carbon–carbon double bond of receptors, leading to clear color change from yellow to colorless.
    Multiple Hydrogen Bonds in the  Self\|assembly of Binaphthol with N\|Containing Compounds
    JI Bao-Ming*, DENG Dong-Sheng, MA Ning, MIAO Shao-Bin, LIU Peng, LI Xian-Fei
    2011, 32(9):  2114-2122. 
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    As a result of mutual recognition, (±)-2,2’-dihydroxy-1,1’-binaphthyl (binol) and various aromatic amines and its derivatives including 4,4’,6,6’-tetramethyl-2,2’-bipyrimidine (4-tmpi), 1,2-bis(4-pyridyl)ethane (4-bpa), trans-1,2-bis(4-pyridyl)ethene (4-bpe) 4,4’-bipyridine-N,N’-dioxide (4-bpo), and di-2-pyridyl ketone (4-dpk) formed well-defined co-crystals 1, 2, 3, 4 and 5, respectively. The crystal structures of these co-crystals were elucidated and are all stabilized by O-H???O, N-H???O and O-H???N hydrogen bonds. In 1-5, the components form an infinite one-dimensional (1D) polar array. The weak C-H???π and π???π interactions have great role in the crystal and influence the architecture of the crystal structure. So, the co-crystals 1, 2, and 5 exhibit two-dimensional (2D) sheet structures, while the co-crystals 3 and 4 display three-dimensional (3D) supramolecular architectures.
    Novel Hemicyanine Dye as Colorimetric Chemosensor for Hg2+
    2011, 32(9):  2123-2127. 
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    A novel Hg2+-selective chemosensor 3a with hemicyanine as colorimetric reporting group and NSe2 chelating unit as ion binding site was reported. The chemosensing behavior and the binding ability of 3a with metal ions was investigated by UV-Vis spectrometry. Chemosensor 3a shows specific Hg2+-selectivity in CH3CN/H2O (v/v, 1:1). The addition of Hg2+ made the absorption spectrum of 3a appear a new band around 410 nm. In addition, the color change of 3a-Hg2+ from rose red to light orange allows naked-eye detection of Hg2+.
    Synthesis of New [12]aneN3 Compounds and Their Catalytic Cleavage of Phosphodiester
    GUO Zhi-Fo, YAN Hao, LI Zhi-Fen, LU Zhong-Lin*
    2011, 32(9):  2128-2132. 
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    Design, synthesis, and catalytic performance of artificial nucleases is full of challenging and has received intensive study in chemistry. In this work, we report on the synthesis of two new methyl 3,5-dimethylbenzolate derived [12]aneN3 compounds 4a and 4b through high efficient click reactions and their characterization with element analysis, NMR, IR and high resolution MS. The corresponding zinc(II) complexes can greatly promote the cleavage of RNA model phosphodiester 2-hydroxypropyl-4-nitrophenylphosphate (HPNPP) in methanol with an acceleration of 107-fold relative to the background reaction.
    Selective Alkaline Earth Metal Ions Sensing Based on New Iminoanthraquinone Chromoionophores
    HU Shu-Zhen, WANG Xue-Hua, CHEN Chuan-Feng*
    2011, 32(9):  2133-2138. 
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    A couple of new chromoionphores 1 and 2 based on iminoanthraquinone derived crown ether were synthesized. Compound 1 showed remarkable color changes in the presence of Ba2+ and Ca2+, while 2 showed high sensitive and selective ‘naked-eye’ recognition toward Mg2+ over other tested ions.
    Mercury Selective Sensor Based on C3v Symmetric Calix[6]arene Tripod
    HE Song, LU Yang, LI Yuan-Yuan, LU Yan*, ZENG Xian-Shun*
    2011, 32(9):  2139-2144. 
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    Three new fluorescent probes based on C3v symmetric calix[6]arene functionalized with three anthracylselenoalkoxy (1), anthracyltelluroalkoxy (2) or anthracylthiaalkoxy (3) groups were synthesized, respectively. The photophysical behavior and the binding ability of 1-3 with some alkaline metal ions and transition metal ions were investigated by fluorescence spectrometry. Receptor 1 exhibited highly selective fluorescence quenching behavior towards Hg2+ in CH2Cl2 with Ka = (1.12 ? 0.08) ? 105 M-1. In addition, the color change of 1-Hg2+ from colorless to light yellow allows naked-eye detection of mercury (Ⅱ)
    Synthesis, Structures and Self-assemblies of Tripodal Malonate, β-Diketones and Pyrazolyls Derivatives
    HU Cong, MA Ming-Liang, LI Xiao-Yan, HU Wen-Jing, ZHAO Xiao-Li, WEN Ke*
    2011, 32(9):  2145-2151. 
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    Tripodal 1,3,5-tris(2-methylenemalonic acid)-2,4,6-triethyllbenzene derivatives 2-5, 1,3,5-tris(2-methylenepentane-2,4-dione)-2,4,6-triethyllbenzene 6 and 1,3,5-tri((3,5- dimethyl-1H-pyrazol-4-yl)methyl)-2,4,6-triethylbenzene 7 have been synthesized. 1H NMR spectra of these compounds are in accord with that they are all in high levels of symmetry. Single crystal X-ray structure analysis revealed that they all adopt an 1,3,5-alternate conformation with the three functional arms reside on one side of the benzene plane, and the three ethyl groups are placed on the opposite side of the benzene plane. Intermolecular hydrogen-bond interactions are the major driving force for the solid state assembly of the compounds with malonic acid (4), malonamide (5), as well as 3,5-dimethyl-1H-pyrazolyl (7) functions. However, No molecular capsules were formed by these compounds via intermolecular hydrogen-bond interactions in the solid state. The interaction of copper(II) ions and pyrazolyl-containing compound 7 (L) resulted in the formation of a discrete cylindrical cage-like complex (Cu3L2) 8 via C-N coordination bonds by the connection of three Cu2+ ions and six pyrazolyl nitrogen atoms from two 7 ligands. The two ligands 7 in complex 8 are in a cis,cis,cis-conformation and a face-to-face orientation.
    Synthesis and Characterization of  Sulfobutylether-β-cyclodextrin/Fe3O4 Hybrid Magnetic Nano-composite
    CAO Li-Yan, WANG Hai-Xia, SHI Juan, ZHOU Ye-Hong, LIU Wen-Juan, ZHANG Guo-Mei, SHUANG Shao-Min*
    2011, 32(9):  2152-2156. 
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    A novel magnetic nano-composite from the combination of Fe3O4 magnetic nanoparticles(MNP) and sulfobutylether-β-CD(SBE-β-CD) has been developed. Fabrication of   composite SBE-β-CD/Fe3O4 MNP is based on conjugating the citrate-modified SBE-β-CD onto the gum arabic-modified MNP via carbodiimide activation. The structural property, morphology and hydrodynamic diameter distribution were characterized by X-ray diffraction(XRD), transmission electron microscopy(TEM) and dynamic light scattering(DLS), respectively. The SBE-β-CD grafting was confirmed by Fourier transformation\|infrared spectrometry(FTIR). The amount of SBE-β-CD grafted on   MNP and the number of SBE-β-CD molecules immobilized on each MNP were determined by thermogravimetric analysis(TGA).
    Synthesis of Cationic Lipids Containing Bis\|cyclen Units and Interaction with DNA
    CHEN Hong, LIAO Yi-Le, HUANG Qing-Dong, WU Jiang*, YU Xiao-Qi*
    2011, 32(9):  2157-2161. 
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    The clinical success of gene therapy requires a safe and effective gene delivery system. Cationic lipids have particularly excellent potential for gene delivery applications because of their lesser immunogenic nature, robust manufacture ability to deliver large pieces of DNA, and ease of handling and preparation techniques. In this study, two bis-cyclen-based cationic lipids were designed and synthesized, and their structures were characterized by 1H NMR and HRMS. Liposomes were easily prepared by mixing cationic lipids with DOPE. Agarose gel electrophoresis demonstrated that the liposomes could completely condense DNA at N/P ratio of 6. The results suggested that the synthesized cationic lipids might be of potential as non-viral gene carrier.
    Hydrogen-bonding-mediated Dynamic Covalent Synthesis of Two Chiral Capsular Compounds
    XU Xiao-Na, WANG Lu, ZHAO Xin*, LI Zhan-Ting*
    2011, 32(9):  2162-2168. 
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    Two chiral two-layered capsular compounds have been synthesizied from chiral cyclohexane-1,2-diamine-derived dipodal precursors. The precursors bear both amino and aldehyde groups which are connected to two intramolecularly hydrogen bonded foldamer segments. Intramolecular hydrogen bonding facilitates the selective generation of two macrocyclic moieties by forming six imine bonds.
    Selective Binding and Fluorescent Behavior of Metal Ions by Podand Possessing Quinoline and Triazole Groups
    YANG Dong-Rui, ZHANG Zhi-Jun, ZHANG Heng-Yi, LIU Yu*
    2011, 32(9):  2169-2174. 
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    Fluorescent chemosensors based on supramolecular interactions are receiving increasing attention due to their potential in analytical chemistry and environmental monitoring. Podands possessing 8-hydroxyquinolino and triazole groups were synthesized via “click chemistry” reaction. Their spectrometric behaviors and the binding ability toward metal ions were investigated by fluorescence, UV-vis spectrum and NMR spectroscopy. With good water solubility, chemosensors 1 and 2 exhibited a distinct switch-on fluorescence response to Cd2+ and Zn2+ over other metal ions, according to which the chemosensory function are realized. Significantly, spectrophotometric studies also demonstrated that the proportion of methanol in aqueous solution greatly influent the selectivity and fluorescent emission ability of host compound. Additionally, 1H NMR analysis revealed that the 8-hydroxyquinolino and the triazole group, as well as the ether chains, were involved in the bonding interactions with the ions.
    Solvent-directing Supramolecular Assemblies of Mn4-thiacalix[4]arene
    BI Yan-Feng, LIAO Wu-Ping
    2011, 32(9):  2175-2180. 
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    Two tetranuclear compounds, Mn4(T4A)2 (1) and Mn4(T4A)2 (DMF)2(2) (T4A = thiacalix[4]arene), were synthesized via the solvothermal reaction of manganese (II) acetic and thiacalix[4]arene with different solvents. Single-crystal analysis reveals that compound 1 with a two-dimensional Kagomé lattice was obtained with the mixed CHCl3/CH3OH solvent, while the interpenetrated 2D compound 2 was synthesized in the mixed DMF/CH3OH solution. Porous compound 1 has some large solvent accessible voids while compound 2 has an impacted extended structure.

    Syntheses, Crystal Structures and Properties of Three New Complex Constructed from 3,5-Dinitrobenzoic Acid and Imidazole with Zn(Ⅱ), Cu(Ⅱ) and Co([Ⅱ)
    ZHANG You-Ming, ZHANG Qin-Sheng, LIN Qi, CAO Cheng, LU Yan-Yun, WEI Tai-Bao*
    2011, 32(9):  2181-2186. 
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    Three complexes with 3,5-dinitrobenzoic acid (DNBC) and imidazole (Im) ligands Zn(DNBC)2(Im)2 (1), Cu(DNBC)2(Im)(H2O) (2), Co1.5(DNBC)4(Im)(CH3OH) (3) were synthesized in water-methanol mixture solution and characterized by elemental analysis, IR spectra. Their crystal structures were determined by single crystal X-ray diffraction. The c complex 1 possesses tridimensional netlike supramolecular structure which is formed by intermolecular hydrogen bonding and Van der Waals force, where each Zn(II) is in 2O+2N coordination modes, each four-coordinated Zn(II) ions form a distorted tetrahedral geometry. The complex 2 has a 1D zigzag chain networks, where each Cu(II) is in 4O+N coordination modes, and each five-coordinated Cu(II) ions form a distorted square-pyramidal geometry. The complex 3 crystallizes in the monoclinic system with space group P2(1)/n, a = 1.20876(7)nm, b = 2.63287(16)nm, c = 1.36466(9)nm, V = 4.3045(5)nm3, Z = 4, F(000) = 2166, the adjacent Co…Co distance of 0.3587nm. Complex 3 possesses 1D zigzag chain composed by Co(II) and by μ-OH2, while triple-clear of octahedral Co(II) bridged by μ-OH2 further connected through the hydrogen bonding to adjacent triple-clear Co(II). Thus, the aggregation of the coordination units through O–H…O hydrogen bonds, results in the formation of channels, which are occupied by imidazole molecules and methanol molecules. Magnetic measurements of complex 3 indicate antiferromagnetic interactions between adjacent Co(II) ions within the trimer.
    Synthesis and Crystal Structure of Four Silver Complexes with 1,2-Bis(2-amino-phenoxy)ethane
    ZHANG Qi-Long, ZHANG Yun-Qian, ZHU Bi-Xue*
    2011, 32(9):  2187-2192. 
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    The four complexes were synthesized from the reaction of 1,2-(2-aminophenoxy)ethane with AgX (X=PF6-, CF3SO3-, NO3- and AgSbF6-) respectively, and characterized by elemental analysis, FTIR and single crystal X-ray diffraction. The results of structural analysis indicate that both complexes 1 and 2 are dinuclear silver (I) complexes, while both complexes 3 and 4 are coordination polymers. The complex 1 is a cryptand, and 2 is a torsional structure formed by Ag-Ag bridging, 3 is 1D zigzag chain, and 4 is 3D porous frameworks. In the four complexes, the inorganic counter anion don’t coordinate with Ag(I).
    Syntheses and Structures of Silver(Ⅰ) Complexes with New Tripodal Ligand Containing Propanenitrile and Imidazolyl Groups
    CAI Kai, WANG Yuan-Yuan, ZHOU Xin, QI Zhao-Peng, WANG Peng, SU Zhi, SUN Wei-Yin*
    2011, 32(9):  2193-2197. 
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    New coordination complexes {[AgL]X}n (X = BF4-, 1a; X = ClO4-, 1b) and {[Ag(L)2]ClO4}n (2) were synthesized by reactions of corresponding silver(I) salt with new tripodal ligand 3,3'-[3-(1H-imidazol-1-yl)propylazanediyl]dipropanenitrile (L) under ligand to metal ratio of 1:1 and 2:1, respectively, and their structures were determined by single crystal X-ray diffraction, electrospray mass spectrometry. Complexes 1a and 1b have one-dimensional (1D) chain structure while complex 2 is mononuclear one. The results show that the metal to ligand ratio has subtle influence on structure of the complexes.
    Synthesis, Crystal Structure and Electrochemical Behavior of Two New Multi\|copper\|containing Heteropolyoxotungstates
    LIANG Chang, FU Hai, LU Ying, LI Yang-Guang, WANG En-Bo*
    2011, 32(9):  2198-2203. 
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    Two new multi-copper-containing polyoxotungstate [Cu(en)2]6[Cu4(SiW9O34)2] 7H2O (1) and [Cu(en)2H2O]2[Cu(en)2]4[CuSiW11O39]2 7H2O (2) have been hydrothermally synthesized. The diffraction analysis reveals that the compound 1 represents the organic-inorganic hybrid based on the sandwish-type polyoxometalates linked by transition-metal coordination cations. The framework of 2 is a two-dimensional net-texture structure with vacancies in it, and the 2D layers are arranged in a parallelstaggering fashion to form a 3D supermolecules framework. It represents a 3D organic–inorganic hybrid based on the bimolecular Keggin polyoxometalates.
    2D and 3D Supramolecular Assemblies from Bis(dipyridylamine) Ligands: Syntheses and Crystal Structures
    DING Cai-Xia, ZENG Fan-Hua, WANG Cheng, NI Jia, NG Seik-Weng, XIE Yong-Shu*
    2011, 32(9):  2204-2209. 
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    Starting from two bis(dipyridylamine) ligands containing 4,4'-dipyridylamine moieties, two novel coordination polymers, [CdL1Br2]n?n7.5H2O (L1 = N,N,N′,N′-tetrakis (4-pyridyl)-1,4-phenylenediamine) (1) and [Cu2L2(μ1,1,3-SCN)2]n?nMeOH (L2=N,N-di (2-pyridyl)-N',N'-di(4-pyridyl-1,4-phenylenediamine) (2), have been prepared under solvothermal conditions. They were characterized by elemental analyses, IR and X-ray single-crystal diffraction measurements. In complex 1, L1 utilizes all its pyridyl nitrogens to coordinate with four Cd(II) centers to afford a three-dimensional (3D) supramolecular assembly containing Kagome structures. Complex 2 has a 2D sheet structure composed of [CuSCN]∞ columns and bridging L2 ligands with SCN- coordinated in a rare μ1,1,3-bridging mode. It is noteworthy that the 2,2'-dipyridylamine unit of L2 is unexpectedly left noncoordinated.
    Preparation of Selective Modified Electrode Based on β-CD Functionalized  Ordered Mesoporous Materials
    XU Shuai, ZHANG Xin, DUAN Shuo, XU Xiao-Meng, ZHOU Chang-Li*
    2011, 32(9):  2210-2214. 
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    A novel modified carbon paste electrode (CD-SBA15/CPE) with β-CD-functionalized SBA-15 mesoporous silica(CD-SBA15) were fabricated and characterized. The recognition mechanism of Nitrophenol , Chloronitrobenzene and Dihydroxybenzene isomers have been studied at the modified electrode using cyclic voltammetry (CV)and differential pulse voltammetries(DPV).The experiment results indicated that o-,m-,p-Nitrophenol , o-,p-Chloronitrobenzene and o-,p-Dihydroxybenzene isomers could be identified entirely at the CD-SBA15/CPE, respectively. The detection sensivity of CD-SBA15/CPE were increased resulting from the unique structure and chemical properties of SBA15, the anodic or cathodic peak resolution of the isomers electrochencal reaction products was increased resulting from the superamolecular recognition of β-CD. The modified electrode might be applied in the practical field.
    Cucurbiturils as a New Coating Materials for Solid Phase Microextraction
    JIANG Yu-Ling, QI Mei-Ling*, FU Ruo-Nong
    2011, 32(9):  2215-2218. 
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    Cucurbiturils (CB) were investigated as a new coating materials for solid phase microextraction (SPME) and were used for the extraction of the volatile components in round cardamon seed followed by gas chromatography. The preparation method for CB[6] SPME is simple, rapid and provides thermally stable layer with good repeatability for multiple extraction. To evaluate the extraction capability of CB[6] SPME, steam distillation and commercial SPME fibers of PDMS/ CAR and PDMS/DVB were also used for comparison. The results show that CB[6] SPME can extract similar components to SD and the commercial fibers, but achieve higher relative peak area percent for the late-eluted components, which is probably originates from the specific molecular structure and interactions of cucurbiturils with analytes of interest. The present work demonstrates the great potential of cucurbiturils as a new type of SPME coating materials.
    Colorimetric Detection of Cr3+ in Aqueous Solution by Thiacalix[4]arene Tetrasulfonate Modified Gold Nanoparticles
    SUN Zhong-Yue, ZHENG Qiu-Ling, LI Hai-Bing*
    2011, 32(9):  2219-2222. 
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    Thiacalix[4]arene tetrasulfonate modified gold nanoparticles which were used as a colorimetric probe for detection of metal ions were synthesized in situ by one step without external reducing agent. The results show that thiacalix[4]arene tetrasulfonate modified gold nanoparticles is capable to detect CrP3+P with high selectivity, and the detection limit is 1μM.
    Effects of Inclusion Complexation and Degree of  Protonation on Cloud Point of Poly(N-acryloyl-N′-propylpiperazine)
    GUO Kai, SUN Liang, WU Meng-Chun, WANG Shao-Dan, WANG Li-Yan*
    2011, 32(9):  2223-2226. 
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    Poly (N-acryloyl-N'-propylpiperazine) (PAcrNPP) is a pH- and temperature-responsive homopolymer. Degree of protonation of PAcrNPP can be changed by adjusting pH of the solution. Cloud point of PAcrNPP increased with increasing degree of protonation. We investigated effects of different sizes of cyclodextrins (CD) on cloud point of PAcrNPP. It was found that α-CD showed a significant effect on cloud point of PAcrNPP while α-CD had almost no effect on its cloud point. At pH 9.0 and pH 7.4, we measured cloud points of PAcrNPP solutions containing different concentrations of α-CD. Cloud point of PAcrNPP solutions rises with increase of concentration of α-CD. Further more, we deduced an equation on the basis of contributions of different forms of PAcrNPP to cloud point. This equation describes the combined effect of complexation of CD and degree of protonation on cloud point from the viewpoint of chemical equilibrium.
    Preparation of β-Cyclodextrin Functionalized Polyacrylonitrile Nanofibers and Its Adsorption for Methylene Blue
    ZHANG Wang, CHEN Ming, DIAO Guo-Wang*
    2011, 32(9):  2227-2230. 
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    A novel Polyacrylonitrile/β-cyclodextrin (PAN/β-CD) nanofibrous membrane (PAN/β-CDnfm) for molecular adsorption was successfully prepared by electrospinning from a homogeneous solution of β-CD and PAN in DMF. PAN/β-CDnfm with the different weight % of β-CD (0 wt.%, 10 wt.%, 30 wt.%, 60 wt.%) was characterized by scanning electronic microscopy, Fourier transform infrared spectroscopy and X-ray powder diffraction. The SEM results showed that the increasing concentration of β-CD in the fibrous membrane improved the fibrous morphology. The viscosity and conductivity of electrospinning solutions were influenced by the addition of β-CD. The studies of FTIR and XRD were proved that β-CD molecules were combined with the PAN nanofibers. In the adsorption study, methylene blue (MB) was used as a model molecule. By UV-vis spectra, PAN/β-CDnfm showed the efficient adsorption ability for MB via the formation of inclusion complexes with β-CD, which indicated that the β-CD functionalized nanofibers may be utilized in purification/separation processes, electrochemical sensor, drug delivery, and so on.