Catalytic epoxidation of olefin over supramolecular compounds of molybdenum oxide clusters and a copper complex

The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0.5] （2） （bipy = 4,4＇-bipyridine, bix = 1,4-bis（imidazole-1-ylmethyl）benzene）. Both compounds were catalytically active and stable for the epoxidation of cyclooctene, 1-octene, and styrene with tert-butyl hydroperoxide （t-BuOOH） as oxidant. The excellent catalytic performance was attributed to the presence of stable coordination bonds between the molybdenum oxide and copper complex, which resulted in the formation of easily accessible Mo species with high electropositivity. In addition, the copper complex also acted as an active site for the activation of t-BuOOH, thus im- proving these copper complex-modified polyoxometalates.

Hydrothermal Synthesis,Crystal Structure and Thermal Stability of a Supramolecular Lead(II) Complex with 4-Nitrobenzoic Acid and 1,10-Phenanthroline

A new complex [Pb（phen）2（4-NBA）]2·2（NO3）·H2O（phen = 1,10-phenanthroline,4-NBA = 4-nitrobenzoate） has been hydrothermally synthesized and structurally determined by single-crystal X-ray diffraction,elemental analyses and IR spectroscopy.The complex crystallizes in monoclinic,space group P21/c with a = 13.416（3）,b = 14.065（3）,c = 16.845（3）（A°） ,β = 110.55（3）o,V = 2976.5（10）（A°）^3,Z = 2,Dc = 1.796 g/cm^3,F（000） = 1564,GOOF = 0.962,the final R = 0.0686 and wR = 0.1746.The crystal structure shows that the lead ion is coordinated with two carboxylate O atoms from the 4-NBA anion,and four N atoms from two phen molecules,forming a slightly distorted pentagonalbipyramidal coordination geometry.It is further extended by various supramo-lecular interactions to form a three-dimensional supramolecular network.The TG analysis result shows that this complex begins decomposing at 30 ℃ and decompounding completely at 733 ℃.

Supramolecular Terbium-SIP Complex Pillared by 4,4'-Bipyridyl,{[Tb(SIP)(H_2O)_5]_2(bpy)_3(H_2O)}n:Synthesis,Crystal Structure and Photoluminescence

The supramolecular terbium complex, {[Tb（SIP）（H2O）5]2（bpy）3（H2O）}n （NaH2SIP = 5-sulfoisophthalic acid monosodium salt and bpy = 4,4＇-bipyridyl）, has been synthesized by the hydrothermal reaction of Tb4O7 with NaH2SIP and bpy at 165 ℃, and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectrum, powder X-ray diffraction and photoluminescence spectrum. It crystallizes in a monoclinic system, space group C2/c, with a = 30.6840（1）, b = 10.9206（2）, c = 17.4967（3） A, β= 111.931（1）°, V = 5438.65（14） A^3, Z = 4, C46H52N6O25S2Tb2, Mr = 1470.90, Dc = 1.796 g/cm^3, p = 2.747 mm^-1, F（000） = 2928, the final R = 0.0654 and wR = 0.1322 for 3806 observed reflections with I 〉 2σ（I）. In the neutral [Tb（SIP）（H2O）5]2 motif, the Tb（III） ions are linked by the SIP ligands to form a one-dimensional zigzag chain propagating along the c axis. The zigzag chains are linked together by hydrogen bonds and π-π stacking interactions to form a two-dimensional supramolecular framework. The uncoordinated bpy molecules act as pillars to extend the two-dimensional sheets into a distinctive pillared three-dimensional supramolecular structure through O-H...N hydrogen bonds. The photoluminescence of the complex was investigated at room temperature in the solid state.

Synthesis,Structure and Thermal Property of a Cobalt Supramolecular Complex Containing N-[(4-Carboxyphenyl)-sulfonyl]glycine

Utilizing N-[（4-carboxyphenyl）-sulfonyl]glycine （abbreviated as cbsglyH3）,a new cobalt complex [Co（cbsglyH）（bipy）2]3H2O （bipy = 2,2＇-bipyridine） has been synthesized under mild conditions and characterized by IR,elemental analysis,thermogravimetric analysis and X-ray diffraction analysis. It crystallizes in the monoclinic system,space group C2/c with a = 34.978（3）,b = 12.0437（11）,c = 20.0041（19） ,β = 122.2990（10）°,V = 7123.0（11） 3,Z = 8,C29H28CoN5O9S,Mr = 681.55,μ = 0.593 mm-1,Dc = 1.271 Kg/m3,F（000） = 2816,the final R = 0.0434 and wR = 0.1351. The title complex is a monomeric compound which is further assembled by intermolecular hydrogen bonds into a 3-D supramolecular network. Thermogravimetric analysis illustrates that this complex begins decomposing at 100 ℃ and decompounding completely at 560 ℃.

Synthesis,Crystal Structure and Water Vapor Adsorption Property of a New Supramolecular Architecture

A new complex, [Cu（HL）（phen）（H2O）]·4H2O（1, H3L·HCl = 5-（（4-carboxypiperidin-1-yl）methyl）isophthalic acid hydrochloride, phen = 1,10-phenanthroline）, has been hydrothermally prepared and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and PXRD. Complex 1 crystallizes in monoclinic, space group P21/c with a = 14.5520（14）, b = 12.6659（12）, c = 15.5006（14） A, β = 97.224（2）o, V = 2834.3（5） A3, Z = 4, C27H33N3O11 Cu, Mr = 639.10, Dc = 1.498 g/cm3, μ = 0.837 mm-1, S = 1.047, F（000） = 1332, the final R = 0.0423 and w R = 0.1118 for 18772 observed reflections（I 〉 2σ（I））. The compound is a Cu（Ⅱ） centre mononuclear molecule in the asymmetric unit. The independent binuclear [Cu2（HL）2（phen）2] units are bridged to form a three-dimensional（3D） supramolecular polymer by extensive hydrogen bonds and π-π non-covalent bonding interactions. Moreover, thermogravimetric（TG） analysis and gas adsorption property of 1 were also discussed.

Preparation for Supramolecular Complexes of Chiral Diols BDPDD, DMBDPD and BINOL with Some Prochiral Compounds

Interaction between chiral diols BDPDD, DMBDPD and BINOL with prochiral compounds was examined and some new supramolecular complexes were prepared. It was found that these chiral hosts could include prochiral guests, a, b-unsaturated compounds or piper- azinedione derivatives to give inclusion crystals in different molar ratio. Formations of these supramolecular complexes were characterized by the data of IR and 1H NMR spectra.

Novel Properties of Supramolecular Complexes Formed by Pairing Cationic Porphyrin and Anionic Metal-Oxo Cluster

MTBPyP (meso-tetrakis(4-N-benzylpyridyl)porphyrin, M=H-2, Zn) bearing positive charge has been shown to associate with SiW12O404- in water solution. The spectral evolution and Job's plots analyses reveal that the relatively stable aggregates contain equal numbers of MTBPyP4(+) and SiW12O404-.

Organic Melt Crystallization as a Method for Synthesis of Supramolecular Complexes

The most simple method for solventless synthesis of supramolecular complex of CMCR·2BPY·BZP, [CMCR = C-methylcalix[4]resorcinarene, BPY = 4,4'-bipyridine, BZP = benzophenone], is proposed. Although CMCR by itself is high melting point compound (above 300°C), CMCR was found to be dissolved in melt mixture of BPY and BZPeven below 120°C. In the mixture of the three components, the reaction occurs to form CMCR·2BPY·BZP supramolecular complex.

Supramolecular complex glycoconjugate vaccine generates self-enhancement effects for carbohydrate antigen delivery

Targeting delivery of tumor-associated carbohydrate antigen(TACA)-based vaccine to antigen-presenting cells(APCs)mediated by endogenous antibodies can improve the immunogenicity of TACA.However,an essential requirement of this approach is to generate high titers of endogenous antibodies in vivo through pre-immunization,which complicates the immunization procedure and may cause side effects.Herein,we report a new generation of APC-targeting TACA-based supramolecular complex vaccine,assembled by sialyl Thomsen-nouveau-bovine serum albumin-adamantine(sTn-BSA-Ada)and heptavalent rhamnose(Rha)-modifiedβ-cyclodextrin(β-CD)via host-guest interaction.The complex vaccine retained anti-Rha antibodies recruiting capability and facilitated the APCs uptake of the vaccine via the interaction of the Fc-domain with the Fc receptors on APCs.We demonstrate that direct immunization of complex vaccine elicited anti-Rha and anti-sTn specific immune response synchronously,generating a novel self-enhancement effect that can improve the antigen delivery to APCs in high efficacy.The structure-activity relationship(SAR)study proved that complex vaccine 4 with polyethylene glycol 6(PEG 6)linker in host molecule provoked a robust and specific sTn immune response comparable to the pre-immunization approach.The antisera induced by complex vaccine,either through direct immunization or pre-immunization,exhibited equal potency of cytotoxicity against the sTn expression cancer cells.This study provides a general platform for TACA-based vaccines with self-enhancement effects without the need for pre-immunization.

One Novel Mn(Ⅱ)Complex with 1-Substituted-1H-1,2,3-triazole-4-carboxylic Acid:Crystal Structure,Fluorescence and Hirshfeld Surface Analysis

The crystal structure of one novel Mn（II） complex, [Mn（pmta）_3]_2[Mn（H_2O）_6]·4H_2O（1）, is reported（Hpmta = 5-methyl-1-phenyl-1H-1,2,3-triazole-4-carboxylic acid）. In the title compound, the asymmetric unit consists of a [Mn（pmta_）3]ˉ anion, half [Mn（H_2O）_6]^（2＋） counter cation and two lattice H_2O molecules, and the intra- and intermolecular hydrogen bonds connect the complex into a supramolecular structure. The liquid-state fluorescence spectra of complex 1 have been determined. Hirshfeld surface analysis was also studied. The main intermolecular interactions in the complex are O···H and H···H contacts.

A SIMPLE METHOD FOR THE INCORPORATION OF LOW MOLECULAR WEIGHT DYES IN ULTRATHIN FILMS

A simple method for the fabrication of ultrathin films containing low molecular weight dye material is introduced(post-adsorption technique). The chromophore used is 4-nitro-4'-decyloxy azobenzene quaternary ammonium salt (azo-10Q).In classical layer-by-layer (LBL) procedures, where the substrate is dipped alternately into the chromophore solution and thecomplementary polyelectrolyte, the chromophore tends to desorb from the film during subsequent immersion in thepolyanion solution, and there is little or no indication of multilayer growth. The extent of desorption depends somewhat onthe selection of polyelectrolyte, the ionic strength and the pH of solution. An alternative approach is to first prepareconventional LBL films from a pair of oppositely charged polyelectrolytes, and then to soak this film into the chromophoresolution, where adsorption by penetration into the LBL film may take place. In preliminary results, a linear dependence ofUV absorbance on layer number of LBL film thus prepared was found, demonstrating the apparent effectiveness of the post-adsorption technique for the preparation of azo-10Q-containing ultrathin films.

Pseudo-Bonding Interaction between Boron-doped Heterofullerene and Zinc Porphine Predicted by DFT Calculation

Theoretical study on the supramolecular complexes formed between boron-doped het- erofullerene （C59B） and zinc porphine （ZnF）, namely C59B-ZnP and its anion species C59B-ZnP, was performed by density functional theory calculation at wB97XD/6-31G（d） level. Strong interaction between porphyrin and heterofullerene moiety was predicted for these complexes based on geometry and electronic structure analysis. Especially, pseudobonding interaction occurring between the B atom of fullerene and the N atom of porphyrin was predicted to occur in C59B-ZnP complex, but be broken in C59B-ZnP complex. Time-dependent density functional theory calculation manifests the redshift of electron absorption for ZnP upon the interaction with heterofullerene.

Synthesis,Structure and Photoluminescence of a New Ir Complex Based on Pyridine-2,3-dicarboxylic Acid

A new complex Ir（ppy）2（Hpda）（Hppy=2-phenylpyridine, H2pda=pyridine-2,3-dicarboxylic acid） has been synthesized and characterized. According to single-crystal X-ray diffraction analyses, the title complex crystallizes in the monoclinic system, space group P21/n with a=8.5708（10）, b=22.685（2）, c=12.5722（15） , β=96.19（1）°, V=2430.2（5） 3, C（29）H（20）N3O4 Ir, Mr=666.22, Z=4, Dc=1.833 g/cm3, F（000）=1304, μ=5.54 mm（-1）, λ（Mo Kα）=0.71073 , GOOF=1.02, the final R=0.049 and w R=0.119 for 4680 independent reflections with Rint=0.069. The title complex is of mononuclear structure. Intermolecular C–H···O hydrogen bonds and π-π stacking interactions result in the formation of a 3D supramolecular network. Photoluminescent spectra show that one intense emission band with the maximum of 516 nm can be observed in the title complex.

Synthesis,Crystal Structure and PTPs Inhibition of a Zinc(Ⅱ) Complex with N-(4-hydroxybenzyl)-L-serine

The reaction of the reduced Schiff base HL（N-（4-hydroxybenzyl）-L-serine） with Zn（CH3COO）2·2H2O in aqueous solution afforded [Zn（L）2]·3H2O（I）. The complex has been characterized by elemental analysis, FT-IR, powder X-ray diffraction, electrospray ionization mass spectrometry and single-crystal X-ray diffraction. Complex I crystallizes in the orthorhombic system, space group P212121, with a=9.197（2）, b=10.445（2）, c=24.149（5） , V=2319.8（8） 3, Z=4, C（20）H（30）N2O11 Zn, Mr=539.83, Dc=1.546 g·cm3, μ=1.122 mm（-1）, F（000）=1128, GOOF=0.971, the final R=0.0206 and w R=0.0506 for 4346 observed reflections（I ＆gt; 2σ（I））. In complex I, each Zn（II） ion coordinates with three carboxyl oxygen atoms and two amine nitrogen atoms from three L-anions, forming a distorted five-coordinated trigonal bipyramidal geometry. Complex I exhibits a 1D wavy chain structure that is extended by hydrogen-bonding interactions to form a supramolecular network. The bioactivity of the complex as a potential PTPs inhibitor in vitro was investigated, displaying potent inhibition against PTP1B（IC（50）, 0.24 μM） and TCPTP（IC（50）, 0.53 μM） with a moderate selectivity.

Supramolecular complex formation of β-cyclodextrin polymer with substituted salicylic acid or 3-hydroxy-2-naphthoic acid and their electrorheological behaviors

According to the chemical design, electrorheological properties of supramolecular complex from β-cyclodextrin polymer (β -CDP) were discussed. Six supramolecular complexes of β-cyclodextrin polymer with substituted salicylic acid and 3-hydroxy-2-naphthoic acid were synthesized by the solid-phase self-assembly method, and their component and structure were characterized by NMR, FT-IR, UV-vis and the fluorescence analysis. Then the electrorheological properties of their suspensions in silicone oil were investigated under DC electric fields. It was found that the yield stresses of these supramolecular complex ER fluids were 7.3–9.8 kPa at 4 kV/mm in DC electric field, which were enhanced by 34%–72% compared with that of pure β-CDP. Among them, that of β-CDP/3-hydroxy-2-naphthoic acid ER fluid was the highest. It was also found that the ER effect of supramolecular complexes can be controlled by changing different guests. When the substituted group is at phenyl ring, ER behavior can be slightly adjusted by the different substituted groups, their number as well as their position at phenyl ring. This can be proved by the measurement of dielectric properties.

Crystal Structures and Theoretical Calculation of Zn（Ⅱ） and Cu（Ⅱ） Supramolecular Complexes Based on Macrocyclic Triamine Ligand 1,4,7-Triazacyclodecane （tacd）

Two supramolecular complexes [Zn（tacd）2]（C6H8O4）·6H2O（1） and [Cu（tacd）2]Cl2·4H2O（2） were synthesized and characterized by elemental analysis, IR spectra, TGA and single-crystal X-ray diffraction analysis. The crystal structure showed that the metal ions in complexes 1 and 2 had similar coordination circumstance. But for the complex 2, it formed a novel two-dimensional supramolecular network with 12-membered rings and four-membered rings via hydrogen bond interaction. The thermal gravimetric analyses indicated that the two complexes had similar steps of weight-loss. On the basis of experiment, the two complexes were calculated by DFT-B3LYP/6-31G（d） in Gaussian 03. The results of calculation are in good agreement with the experiment.

Visual sensing of picric acid in 100% aqueous media based on supramolecular polythiophene assemblies with colorimetric and fluorescent dual response

A colorimetric and fluorometric dual probe based on a water-soluble polythiophene derivative(PMTPBA)was designed and synthesized.It can be applied to determination of picric acid(PA) in 100% aqueous solution.The approach relies on the formation of supramolecular polythiophene assemblies in the presence of PA through electrostatic,charge transfer and π-π stacking interactions.This probe could be utilized for the rapid and visual detection of PA both in aqueous solution and solid support with high specificity and sensitivity.The detection limit of this sensor is as low as 5.0 × 10^-8 mol/L.

Rare-earth,nitrogen-rich,oxygen heterocyclic supramolecular compounds(Nd,Sm,and Eu):Synthesis,structure,and catalysis for ammonium perchlorate

Three novel rare-earth,nitrogen-rich and oxygen heterocyclic supramolecular complexes,namely[Nd(BTF)_(2)(H_(2)O)_(5)]_(n),[Sm(BTF)_(2)(H_(2)O)_(5)]_(n),and[Eu(BTF)_(2)(H_(2)O)_(5)]_(n),were synthesized.A single crystal was obtained by the solvent evaporation method,and the structure and coordination mode of metal complexes were determined by single crystal X-ray diffraction.Results show that the supramolecular complexes contain many hydrogen bonds and thus have good thermal stability(T_(dec)>540 K).The thermal decomposition of ammonium perchlorate(AP)catalyzed by the complexes was investigated by differential thermal analysis,which reveals a pre-eminent catalytic effect on AP.The high temperature decomposition peak of AP can be advanced by nearly 90 K at the amount of added complexes of 10 wt%,and the activation energy of AP descent range is from 70 to 150 kJ/mol.The other properties were fully characterized through elemental analysis and Fourier transform infrared spectroscopy.

Study of a water-soluble supramolecular complex of curcumin andβ-cyclodextrin polymer with electrochemical property and potential anti-cancer activity

As a member of the curcuminoid compound family,curcumin(Cur)has many interesting therapeutic properties.However,its low aqueous solubility and stability have resulted in poor bioavailability and restricted clinical efficacy.Based on size matching,β-cyclodextrin polymer(β-CDP),with its hydrophilic polymer chains and hydrophobic cavities,can form an inclusion complex with Cur.To improve the water solubility and stability of Cur,a simple and eco-friendly grinding method was designed to formβ-CDP inclusion complexes.According to the Boltzmann-Hamel's method and Job's method,the molar ratio of theβ-CD unit inβ-CDP to Cur was determined to be 1:1.The diffusion coefficient and diffusion activation energy of Cur-β-CDP were calculated in an electrochemical study.This supramolecular complex worked well in vitro to inhibit the proliferation of hepatoma carcinoma cells HepG2.Remarkably,this method visibly reduced the undesirable side effects on normal cells,without weakening the anti-cancer activity of the drugs.We expect that the obtained host-guest complex will provide a new approach for delivering natural drug molecules,having low water solubility.

Virus-like supramolecular assemblies formed by cooperation of base pairing interaction and peptidic association

A peptide nucleic acid （PNA）-peptide conjugated molecule, T＇3（AKAE）2, was designed to have both a PNA segment for oligo- nucleotide binding and an ionic self-complementary peptide sequence for self-association. T＇3（AKAE）2 could co-assemble with oligoadenines （d（A）x） to form virus-like supramolecular structures whose morphology showed dependence on the chain length and rigidity of the d（A）x molecules. Smaller nanospheres with diameters of 13.0±2.0 nm were produced in the case of d（A）6. Wormlike aggregates with lengths of 20-50 nm and diameters of 15.0±2.5 nm were found in the cases of d（A）12, d（A）ls, d（A）24 and d（A）30. And larger spherical aggregates with diameters of 18±5 nm came into presence in the cases of d（A）36 and d（A）42＋. These nanostructures were suggested to be formed under a cooperative effect of base pair recognition and peptidic association. The study provides insights into the programmed assembly of a multi-components system as well as control of the size and shade of the co-assembled structures, which is of great significance in develouing gene/drug deliverv systems.