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01 October 2014, Volume 30 Issue 5

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Chemical Research in Chinese Universities Vol.30 No.5 June 2014 CONTENTS

2014, 30(5):  0-0. 

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Preparation and Visible-light Photochromism of Phosphomolybdic Acid/Polyvinylpyrrolidone Hybrid Film

SUN Yan, WANG Xiansheng, LU Yamei, XUAN Limin, XIA Shuang, FENG Wei, HAN Xiangkui

2014, 30(5):  703-708.  doi:10.1007/s40242-014-4160-5

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The visible-light photochromic hybrid film was constructed by entrapping phosphomolybdic acid(PMoA) into polyvinylpyrrolidone(PVPd) networks. The microstructure, photochromic properties and mechanism were investigated with transmission electron microscopy(TEM), atomic force microscopy(AFM), Fourier transform infrared (FTIR) spectroscopy, ultraviolet-visible(UV-Vis) spectra and X-ray photoelectron spectroscopy(XPS). The results indicate that the Keggin geometry of PMoA and the basic structure of PVPd are not destroyed during the composite process. Irradiated with visible light, the transparent PMoA/PVPd film changes color from colorless to blue and exhibits reversible photochromism in the presence of oxygen. According to the XPS analysis, the charge-transfer bridge of N-H-O has been built between PMoA and PVPd matrix via non-covalent bonding, and the appearance of Mo⁵⁺ species indicates that the photo-reduction process is in accordance with the proton transfer mechanism.



Syntheses, Structures and Properties of Three Transition Metal Coordination Polymers Based on Semi-rigid 3-Pyridylnicotinamide and S/N-Containing Dicarboxylate Mixed Ligands

WANG Xiuli, GONG Chunhua, QU Yun, LIU Guocheng, ZHANG Juwen

2014, 30(5):  709-714.  doi:10.1007/s40242-014-4128-5

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Three new coordination complexes,[Co(L)(ADTZ)]·H₂O(1),[Cd(L)(ADTZ)]·H₂O(2) and[Zn(L)(ADTZ)]·H₂O(3)[L=3-pyridylnicotinamide, H₂ADTZ=2,5-(s-acetic acid)dimercapto-1,3,4-thiadiazole], were synthesized under hydrothermal conditions. These complexes were structurally characterized by single-crystal X-ray diffraction analysis and further characterized by infrared spectroscopy(IR), powder X-ray diffraction (PXRD) and thermogravimetric analysis(TGA). Complexes 1-3 exhibit the similar 2D double-layer networks based on 1D[M-L]_n zigzag chains and 1D[M-ADTZ]_2n double-chains with different distances between metal ions and with various conformations of ADTZ anions. In complexes 1 and 3, the 2D sheets are extended into a 3D supramolecular frameworks by hydrogen bonding interactions. The subtle effects of the central metal atoms on the structures of the title coordination polymers were discussed. The electrochemical properties of complex 1 and luminescent properties of complexes 2 and 3 were investigated. In addition, complexes 1-3 exhibit photocatalytic activity for dye methylene blue degradation under UV light and show good stability toward photocatalysis.



Third-order Optical Nonlinearities of a Series of Compounds Derived from a Keplerate Type Molybdenum-oxide-based Polyoxometalate

ZHOU Yunshan, QU Ningning, WANG Xuan, ZHANG Lijuan, SHI Zonghai, HASSAN ul Sadaf

2014, 30(5):  715-719.  doi:10.1007/s40242-014-4065-3

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By reacting the unique Keplerate type molybdenum-oxide based polyoxometalate (NH₄)₄₂·[Mo₁₃₂O₃₇₂·(CH₃COO)₃₀(H₂O)₇₂]·ca.300H₂O·ca.10CH₃COONH₄(1) with tetramethylammonium bromide, a new derivative (NH₄)₂₆[TMA]₁₆{Mo₁₃₂O₃₇₂(H₂O)₇₂(CH₃COO)₃₀}·ca.7NH₄CH₃COO·ca.189H₂O(2, TMA=tetramethylammonium)was prepared. Compound 2 was characterized by Fourier transform infrared spectroscopy(FTIR), UV-Vis, elemental and thermogravimetric analyses. By the well-established Z-scan technique, investigations on the nonlinear optical(NLO) properties of the series of compounds derived from the Keplerate type molybdenum-oxide-based poly-oxometalate, namely, the newly prepared compound 2, the three previously reported compounds, included compound 1, (NH₄)₁₈(TBA)₂₄{Mo₁₃₂O₃₇₂(H₂O)₇₂(CH₃COO)₃₀}·ca.7NH₄CH₃COO·ca.173H₂O(3,TBA=tetrabutylammonium) and (DODA)₄₀(NH₄)₂[(H₂O)_nMo₁₃₂O₃₇₂(CH₃COO)₃₀(H₂O)₇₂](4, DODA=dimethyldioctadecylammonium), reveal that the third-order nonlinearity[χ⁽³⁾] values of compounds 1, 2 and 3 in the DMF/H₂O solution and compound 4 in chloroform are almost the same, which indicates that the counter cations with different length of alkyl chains show ignorable impacts on the NLO susceptibility. In other words, the remarkable third-order nonlinearities[χ⁽³⁾≈10^-19 m²/V²] mainly come from the[Mo₁₃₂O₃₇₂(CH₃COO)₃₀(H₂O)₇₂]^42- anions. This fact reveals that the applications of the NLO active polyoxometalates in various environments(such as hydrophilic, hydrophobic, polar, apolar, etc.) can be achieved by simply varying cations to meet the demands in the design of diverse devices.



Synthesis and Crystal Structure of 1D Cd-amine Coordination Polymer and Its Luminescent Properties

XU Mengying, LIU Zhigang, FAN Ruiqing, GAO Song, CHEN Shuo, YANG Yulin

2014, 30(5):  720-725.  doi:10.1007/s40242-014-4032-z

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A novel one dimension(1D) cadmium coordination polymer {[Cd(mpda)₃]·2(NO₃)}_n(1) was synthesized via refluxing a mixture of tetradentate Schiff base ligand N,N'-bis(2-pyridinylethylidene)phenylene-1,3-diamine(L) and Cd(NO₃)₂ in acetonitrile, whose structure was characterized by means of single crystal X-ray diffraction, FTIR spectroscopy, elemental analysis and proton nuclear magnetic resonance(¹H NMR). Center metal Cd(II) ion is six-coordinated by six nitrogen atoms from six different m-phenylenediamine(mpda), giving rise to a[CdN₆] octahedral coordination environment. The two adjacent cadmium centers are linked by three mpda molecules leading to the construction of 1D chain structure. The crystal structure is stabilized by N-H···O hydrogen bonds to form three-dimension supramolecule. Compound 1 exhibits intense yellow luminescence in solid state at 298 K(λ_em=554 nm), which shows a blue shift at 77 K(ca. 147 nm). Additionally, fluorescence characteristics of compound 1 were investigated in different solvents(polarity: DMSO>CH₃CN>CH₃OH>CHCl₃>toluene) at 298 and 77 K. The results show that the emission peak of compound 1 in solvent exhibits a slight bathochromic shift. However, the emission peaks of compound 1 in CH₃OH and CHCl₃ are red shift compared with that in CH₃CN. It is revealed that the luminescence behavior of compound 1 depends on not only the polarity of solvent but also the hydrogen bonding properties between solvent and solute. In addition, the emission peak of compound 1 in solution shows a red shift obviously at 77 K than that at 298 K(ca. 144-159 nm), with the fluorescence lifetime increased at 77 K. The lifetime in DMSO at 77 K(τ=12.470 μs) was the longest one. The quantum yield of compoud 1 increases with increasing the polarity of solvent within a range of 1.8%-8.3%.



Global Insight into N-Glycome and N-Glycoproteome of Three Most Abundant Snake Venoms in Asia

CAO Weiqian, HUANG Jiangming, CAO Jing, YANG Pengyuan

2014, 30(5):  726-730.  doi:10.1007/s40242-014-4148-1

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Snake venom is a complex cocktail including a variety of biological active proteins and proteinaceous components, which have considerable medical and pharmacological importance. N-Glycosylation is widely implicated as a common modification in numerous venom proteins and impacts the in vivo venomic functions. However, systematic survey of N-glycome and N-glycoproteome on snake venoms has not been undertaken. In this study, employing combination of N-glycomics and N-glycoproteomics strategies, we explored the N-glycosylation including both N-glycoproteins and N-glyco-chains in three venoms from Agkistrodon blomhoffii, Naja naja atra Cantor and Vipera russelii siamensis Smith, respectively, which are amongst the most abundant venomous snakes in Asia. As a result, numbers of N-glycoproteins and N-glycans were identified. However, the overlaps of N-glycoproteins and N-glycans of the three venoms were small. Thus, the exploration results of N-glycome and N-glycoproteome indicate that N-glycosylation increases the complexity and variety of the three venoms. Our research provided some new horizons for the comprehensive understanding of venoms variation, which is helpful for the basic venom research as well as the management of snake envenomation.



Qualitative and Quantitative Analysis of Drug Interactions: Fritillary Mediating the Transport of Alkaloids in Caco-2 Cells by P-Glycoprotein

MA Jingwei, KAN Hong, MA Yinghui, MEN Lihui, PI Zifeng, LIU Zhiqiang, LIU Zhongying

2014, 30(5):  731-737.  doi:10.1007/s40242-014-4066-2

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Ultra performance liquid chromatographic-electrospray ionization-mass spectrometry(UPLC-ESI-MS) was used to investigate the potential interaction between selected ingredients of Aconitum and fritillary. The efflux ratios of 14-benzoylmesaconine(BM), 14-benzoylaconine(BC), 14-benzoylhypaconine(BH), mesaconitine(MA), aconitine(AC) and hypaconitine(HA) was 11.16, 12.53, 11.69, 12.8, 11.03 and 6.15, respectively, and the secretion of them was inhibited by Verapamil, which means they are the substrates of permeability-glycoprotein(P-gp). The transport of Aconitum alkaloids extract through a Caco-2 cell monolayer was determined in the absence and presence of fritillary extract. And the fritillary extract increased the absorption of Aconitum alkaloids. Peimine(PE) and peiminine(PEN) in fritillary increased the absorption of pure Aconitum alkaloids. The transport of digoxin was respectively enhanced by PE and PEN, which means they are the inhibitors of P-gp. PEN showed more effective inhibition than PE at the same concentration. The in vitro data suggest that the compounds such as fritillary present in alkaloids were able to inhibit the P-gp activity and lead modifying the transport of alkaloids.



Ratiometric Fluorescent Probe Based on Novel Red-emission BODIPY for Determination of Bovine Serum Albumin

SONG Fengling, XUE Yingying, WANG Xu, WANG Jingyun, XIONG Xiaoqing, PENG Xiaojun

2014, 30(5):  738-742.  doi:10.1007/s40242-014-4029-7

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A novel red-emission boron-dipyrromethene(BODIPY) dye with a pyrrole ring was synthesized simply via one-pot reaction. The spectral properties of it were investigated under the conditions of different solvents. The results show that the as-prepared BODIPY dye is extremely sensitive to solvent polarity, and the fluorescent emission enhances with the decrease of solvent polarity. In aqueous buffer, the addition of bovine serum albumin leads to a ratiometric change in absorption spectra with an association constant of 1.16×10⁶ L/mol. Meanwhile, the fluorescence emission increases greatly at 622 nm but changes slightly at 575 nm. The response time is very short(less than 3 min), and the changes of color can be noticed by naked eyes. Bovine serum albumin can be detected by this ratiometric fluorescence probe, but other proteins or enzymes cannot be detected by this method, which indicates that this novel dye has high selectivity towards bovine serum albumin. The reason is that bovine serum albumin has suitable hydrophobic cavities for binding with the dye. In addition, the dye molecule can penetrate cell membrane easily and make a fast fluorescent stain, which makes it a potential probe for living-cell fluorescence imaging.



Construction and Validation of Simple Magnetic Nanoparticle Detector Based on Giant Magnetoresistive Effect

CHENG Chunying, XIN Youying, YIN Xuebo

2014, 30(5):  743-748.  doi:10.1007/s40242-014-4023-0

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The finding of giant magnetoresistive(GMR) effect develops a new field for the sensing application with magnetic nanoparticles(MNPs) labeling. A convenient GMR sensor was built with a permanent magnet to excite the MNPs in this work. The sensing element contained a Wheatstone bridge with the GMR material as one of its branches. The magnetic field from MNPs unbalanced the Wheatstone bridge. After being amplified, the output signals were recorded. The construction and optimization of the magnetoresistive sensing platform were discussed in detail. The detection of three kinds of MNPs validated the performance of the proposed GMR sensor. The sensor showed a fast response to the addition or removal of MNPs. Because of its simplicity, this kind of GMR sensor can be developed in a routine laboratory. The finding of this new GMR sensor will promote the development of the method of probing biomolecules and the study on the biomolecular interaction after being labeled magnetically.



Synthesis and Biological Evaluation of Entecavir 4'-Ester Derivatives

FENG Deri, LIU Jiaan, LIANG Shuang, WANG Yanyan, XU Youjun

2014, 30(5):  749-754.  doi:10.1007/s40242-014-4183-y

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Entecavir can significantly inhibit the replication of HBV-DNA, reduce the HBV-DNA level in blood serum. But suffering from low oral bioavailability, entecavir has low intestinal membrane permeability and poor metabolic stability. In this study, 12 different derivatives of entecavir 4'-ester were regioselectively synthesized and their apical-to-basolateral permeabilities across Caco-2 cells and HBV-DNA inhibitory efficacies were evaluated. Most of the compounds showed high permeabilities across Caco-2 cells compared with entecavir, compounds 5b and 5e also exhibited comparable anti-HBV activities with that of entecavir, especially.



Synthesis and Antimicrobial Activity of Some New 4H-Pyrrolo[1,2-a]benzimidazoles

JIANG Yuliang, HAN Qiaorong, SHEN Ronghua, ZANG Xinxin, WANG Bingxiang

2014, 30(5):  755-758.  doi:10.1007/s40242-014-4147-2

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Some new 4H-pyrrolo[1,2-a]benzimidazoles(2a-2f) have been synthesized. The structures of these compounds were confirmed by IR, ¹H NMR, mass spectroscopy and elemental analysis. Compound 2a was further confirmed by X-ray diffraction. The in vitro antimicrobial activities of these compounds were determined against some gram-positive bacteria, gram-negative bacteria and fungi and their drug-resistant isolates in comparison with standard drugs. Antimicrobial results indicate that compounds 2c, 2d and 2e show moderately active antibacterial properties, their minimum inhibitory concentrations are from 12.5 μg/mL to 125 μg/mL. In the series, the most active compound against C. albicans is compound 2f with an MIC value of 31.25 μg/mL.



Synthesis and Biological Evaluation of Novel 5,7-Diphenylimidazo[1,2-a]pyridine Derivatives

LIAO Huimin, CHONG Lian'e, TAN Li, CHEN Xiaodan, YOU Rui, GONG Ping

2014, 30(5):  759-763.  doi:10.1007/s40242-014-4081-3

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A series of novel 5,7-diphenylimidazo[1,2-a]pyridine derivatives was designed and synthesized. The in vitro cytotoxic activities of all the target compounds against human colorectal cancer(HT-29), human lung cancer(H460), human gastric cancer(MKN45) and human breast cancer(MDA-MB-231) cell lines were evaluated. The pharmacological results indicated thatmost of the target compounds showed moderate to excellent activities against the tested cell lines. The most promising compound 4h(0.20, 0.006, 0.08, 0.021 μmol/L) was 2.6, 5.1, 3.6 and 21.9 times more active than EPC2407(0.52, 0.031, 0.29, 0.46 μmol/L) against HT-29, H460, MKN45 and MDA-MB-231 cell lines, respectively.



Synthesis and Antitumor Activities of 1,3,4-Thiadiazole Derivatives Possessing Benzisoselenazolone Scaffold

ZHAO Jie, XUAN Lina, ZHAO Haichuan, CHENG Ji, FU Xiaoyun, LI Sha, JING Fen, LIU Yuming, CHEN Baoquan

2014, 30(5):  764-769.  doi:10.1007/s40242-014-4080-4

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A series of novel 1,3,4-thiadiazole derivatives possessing benzisoselenazolone scaffold were designed and synthesized, and their antitumor activities against human cervix adenocarcinoma(HeLa), human liver cancer cell(SMMC-7721), human breast cancer cell(MCF-7) and human lung cancer cell(A549) lines were evaluated by CCK-8 assay. The bioassay results demonstrate that most of the tested compounds showed potent antiproliferative effects against various cell lines. Furthermore, compounds 7c, 7e, 7h, 7i and 7k showed significant antiproliferative activities against SMMC-7721 cells, with IC₅₀ values of 2.38, 2.67, 1.35, 2.75 and 2.48 μmol/L, respectively. Compounds 7a, 7e, 7j and 7lexhibited highly effective antitumor activities against MCF-7 cells, with IC₅₀ values of 2.89, 2.95, 1.12 and 2.75 μmol/L, respectively. Compound 7j was found to be the most potent compound against A549 cells, with an IC₅₀ value of 1.25 μmol/L. The pharmacological results suggest that the substituents of benzylthio-moiety at position 2 on 1,3,4-thiadiazole are vital for modulating antitumor activities against various cancer cell lines.



Stereoselective Synthesis of (R)-Salmeterol via Asymmetric Cyanohydrin Reaction

LI Wei, HUANG Hai, JIN Xiaodong, LIU Yujian, XU Chaohang, ZHU Hongjun

2014, 30(5):  770-773.  doi:10.1007/s40242-014-4073-3

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The authors described a short and highly enantioselective route to (R)-salmeterol involving asymmetric synthesis of cyanohydrin followed by nucleophilic substitution with 6-(4-phenylbutoxy) hexyl methanesulfonate.



Regioselective Acylation of 2'-or 3'-Hydroxyl Group in Salicin: Hemisynthesis of Acylated Salicins

SHAO Chen, PEI Yuxin, BORG-KARLSON Anna-Karin, PEI Zhichao

2014, 30(5):  774-777.  doi:10.1007/s40242-014-4041-y

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Salicin-based phenolic glycosides(PGs) are important defensive substances against herbivore feeding and have good bioactivities. In this work, a novel approach for the synthesis of salicin-based PGs has been developed, by which PGs of 2'-O-acetylsalicin(5a), 3'-O-acetylsalicin(5b) and 3'-O-benzoylsalicin(5d) were hemisynthesized. The effects of acylation reagent, solvent and temperature on the regioselective acylation of 2'-or 3'-hydroxyl groups of salicin mediated by dibutyltin oxide were investigated. The optimal conditions under which the best regioselectivity reached for 5a-5dwere discovered, respectively. Moreover, a tentative tin-oxygen coordination mechanism was put forward to explain the different regioselectivities shown under different conditions.



A Novel Thermostable β-Galactosidase from Geobacillus kaustophilus HTA42

YU Shanshan, YIN Hongbing, WANG Xinying, FENG Li, XU Chunchun, LI Jing, HAN Hongxiang, LIU Shuying

2014, 30(5):  778-784.  doi:10.1007/s40242-014-4090-2

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A novel thermostable β-galactosidase gene, designated as GkGal1A, from the thermophilic bacterium Geobacillus kaustophilus HTA426 was cloned and heterologously overexpressed in Escherichia coli(E. coli). Based on the sequence analysis, GkGal1A belongs to the glycosyl hydrolase family 1 that was the first β-galactosidase of bacterial origins expressed by us in this family. The apparent molecular weight of GkGal1A determined by sodium deodecyl sulfate-polyacrylamide gel electrophoresis is 52000. It exhibited the highest activity toward p-nitrophenyl-β-D-galactopyranoside at pH 7.8 and 70℃ and displayed high thermal stability. Divalent cations are prerequisite for the activity of GKGal1A, with the highest activity in the presence of Mn²⁺. Moreover, the three-dimensional structure of GkGal1A was modeled to speculate the structure of the catalytic residues and the reaction mechanism. The catalytic residues consisting of Glu166 and Glu355 were verified by site-directed mutagenesis.



3-Oxodapagliflozin as a Potent and Highly Selective SGLT2 Inhibitor for the Treatment of Type 2 Diabetes

ZHANG Shuo, WANG Yuli, LIU Wei, XIE Yafei, LIU Yuqiang, XU Weiren, TANG Lida, WANG Jianwu, ZHAO Guilong

2014, 30(5):  785-793.  doi:10.1007/s40242-014-4043-9

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Structural modifications of 3-OH in the glucose moiety of dapagliflozin(1), an approved potent sodium-dependent glucose transporter 2(SGLT2) inhibitor, led to 3-oxodapagliflozin(16), a highly potent and more selective SGLT2 inhibitor[IC₅₀(hSGLT1)/IC₅₀(hSGLT2)=2851 for compound 16 vs. 843 for compound 1]. 3-Oxodapagliflozin(16) exhibited in vitro(IC₅₀=1.0 nmol/L against hSGLT2 for compound 16 vs. 1.3 nmol/L for compound 1) and in vivo activities comparable to those of dapagliflozin(1). The bioactivities of 3-oxodapagliflozin (16) warrant its further evaluation as a promising SGLT2 inhibitor for the treatment of type 2 diabetes.



Electronic Properties of BaTiO₃ (110) Polar Terminations

XIE Ying, YU Haitao

2014, 30(5):  794-799.  doi:10.1007/s40242-014-4174-z

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The band structures, electron density differences, and surface energies of five different BaTiO₃ (110) terminations were investigated by first-principles calculations. According to the calculated results of electron density differences, the bonding characteristics of these considered terminations were discussed. The computational results indicate that the BaTiO-terminated surface is metallic, while the O₂-, O-, Ba-and TiO-terminated surfaces are all insulative. Furthermore, the computed surface energies suggest that for the considered terminations, the polarity compensation achieved through surface reconstruction or surface defect is more effective than by change in surface electronic structure. The defected or reconstructed terminations predominate over cleavage and construction of BaTiO₃ crystal along (110) direction.



Oxygen-evolving SnO₂-based Ceramic Anodes in Aluminium Electrolysis

POPESCU Ana-Maria

2014, 30(5):  800-805.  doi:10.1007/s40242-014-4137-4

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This study deals with SnO₂-based ceramic anodes doped with Sb₂O₃ and CuO, aiming at contributing new data regarding their electrochemical behavior in cryolite melts. The performances of the anodes were evaluated by anodic polarization, cyclic voltammetry, and current efficiency and corrosion measurements. The investigation proves that the anodic process of SnO₂-based inert anodes occurs at a low overvoltage and the oxygen discharge takes place in one step with an exchange of two electrons. The current efficiency and corrosion were proved to be dependent on the electrolysis parameters and composition of electrolysis bath. For a long term electrolysis, the dissolution of the anode in the cryolite-alumina melt produced small aluminium contamination(ca. 0.2%, mass fraction).



Preparation and Electrochemical Performance of Cobalt-free Cathode Material Ba_0.5Sr_0.5Fe_0.9Nb_0.1O_3-δ for Intermediate-temperature Solid Oxide Fuel Cells

LONG Wen, XU Huawei, HE Tianmin

2014, 30(5):  806-810.  doi:10.1007/s40242-014-4130-y

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Perovskite oxide Ba_0.5Sr_0.5Fe_0.9Nb_0.1O_3-δ(BSFN) as a cobalt-free cathode for intermediate-temperature solid oxide fuel cells(IT-SOFCs) on the Ce_0.8Sm_0.2O_1.9(SDC) and La_0.9Sr_0.1Ga_0.8Mg_0.2O_3-δ(LSGM) electrolytes was prepared and investigated. The single phase BSFN oxide with a cubic perovskite structure and relatively high electrical conductivities was obtained after sintering at 1250℃ for 10 h in air. The BSFN cathode exhibited excellent chemical stability on the SDC and LSGM electrolytes at temperatures below 950℃. The area specific resistance of the BSFN cathode on the SDC and LSGM electrolytes were 0.024 and 0.021 Ω·cm² at 800℃, respectively. The maximum power densities of the single cell with BSFN cathode in 300 μm-thick SDC and LSGM electrolytes achieved 414 and 516 mW/cm² at 800℃, respectively. These results show that the BSFN material is a promising cobalt-free cathode candidate to be used in IT-SOFCs. A combination of the BSFN cathode and LSGM electrolyte is preferred owing to its excellent electrochemical performance.



Effect of Particle Conductivity on Fe-Si Composite Electrodeposition

LONG Qiong, ZHONG Yunbo, ZHENG Tianxiang, LIU Chunmei

2014, 30(5):  811-816.  doi:10.1007/s40242-014-4096-9

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Coatings containing Fe-Si or Si particles were electrodeposited on 3.0%(mass fraction) Si steel sheets. The surface morphology, the cross-section and the silicon content of coating have been investigated, respectively. It was found that the number of particles on the coating surface and cross-section significantly decreased with increasing silicon content in the applied particles, leading to a decrease of the silicon content of coatings. About 10.2% silicon content of coatings deposited with Fe-30%Si particles can be obtained, whereas that for Si particles was only 2.9% at a particle concentration of 100 g/L and current density of 2 A/dm². This is mainly attributed to the conductivity of applied particles. High conductivity can promote the co-deposition of the particles. With increasing silicon content in the particles, their conductivity decreased sharply, resulting in the decrease of silicon content of coatings. Present work may initiate a new method to modify the particle content of the composite coatings via changing the conductivity of the particles during the composite electrodeposition. In this paper, a possible mechanism was proposed to explain the phenomena.



Preparation and Characterization of Hydrophobic Nano Silver Film on Butterfly Wings as Bio-template

FANG Yan, SUN Gang, BI Yuhan

2014, 30(5):  817-820.  doi:10.1007/s40242-014-4070-6

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Hydrophobic nano silver films were fabricated on butterfly wings as bio-template. The micrometric/nano structures and hydrophobicity of the surfaces were investigated with the help of scanning electron microscope(SEM) and video-based contact angle meter. The hydrophobic mechanism of silver film was analyzed with the aid of Cassie's formula. On the nano silver films of various thicknesses(5, 10, 20, 40, 60, 80, 100 nm), all the contact angles(CAs) of water were bigger than 120°. When the silver film was 5 nm, the CAs of water on it on the wing surfa-ces of Mimathyma nycteis and Speyeria aglaja were 143.2° and 139.2°, respectively. Coated with the sliver film of the same thickness, butterfly wing surface exhibited the CA remarkably bigger than glass slide surface, exhibiting its high hydrophobicity. With the increase of silver film thickness on butterfly wing surface, the hydrophobicity kept decreasing. The micrometric/nano hierarchical structures on butterfly wing surface result in the transition of metal silver from hydrophilicity to hydrophobicity.



Direct Evidence for the Effect of Intermolecular Hydrogen Bonding on Organogels

MA Jie, WEI Jue, BAI Binglian, TAN Guangtong, WANG Haitao, LI Min

2014, 30(5):  821-824.  doi:10.1007/s40242-014-4062-6

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In order to get direct evidence for the effect of intermolecular hydrogen bonding on the organogels, one amide group in N-(3, 4, 5-octyloxybenzoyl)-N'-(4'-aminobenzoyl)hydrazine(D8) was replaced by a Schiff base group, forming N-(3,4,5-octyloxybenzoyl)-N'-(4'-amidobenzoyl) acylhydrazone(T8SchA). D8 and T8SchA organogels in cyclohexane show the same hexagonal columnar structure. And the hydrogen bonding was demonstrated to be still interacting in the organogels. However, although the molecular geometry of D8 was well retained in T8SchA, the molecular dipole moment of T8SchA is bigger than that of D8 due to the reduction of the number of hydrogen bonds. Thus, the decreased gelling stability of T8SchA compared to that of D8 can only be attributed to the reduction of the number of intermolecular hydrogen bonds, which provides direct evidence that intermolecular hydrogen bonding plays an important role in stabilising organogels.



New Half-sandwich Zirconium(IV) Complexes Containing Salicylaldimine Ligands: Synthesis, Characterizations and Catalytic Properties

LIU Kefeng, YAO Gang, WU Wenlei, GAO Bo

2014, 30(5):  825-830.  doi:10.1007/s40242-014-4054-6

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Two new half-sandwich zirconium(IV) complexes bearing salicylaldimine ligands of the type CpZr[2-^tBu-4-R-6-(CH=NⁱPr)C₆H₂O]Cl₂[R=H(1), ^tBu(2)] were prepared by the reaction of CpZrCl₃ with the corresponding lithium of salicylaldimine ligands 2-^tBu-4-R-6-(CH=NⁱPr)C₆H₂OLi[R=H(LiLa), ^tBu(LiLb)]. Complexes 1 and 2 were characterized by ¹H NMR, ¹³C NMR spectroscopy and elemental analysis. When activated with AlⁱBu₃ and Ph₃CB(C₆F₅)₄, both complexes 1 and 2 exhibited reasonable catalytic activities for ethylene polymerization, producing polyethylenes with moderate molecular weight. Complexes 1 and 2 also exhibited reasonable catalytic activities for ethylene copolymerization with 1-hexene, producing poly(ethylene-co-1-hexene)s with moderate molecular weight and reasonable 1-hexene content.



Theoretical Studies on the Dihydrogen Bonding Between Shortchain Hydrocarbon and Magnesium Hydride

LI Li, BAI Fuquan, ZHANG Hongxing

2014, 30(5):  831-836.  doi:10.1007/s40242-014-4051-9

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The C-H×××H dihydrogen-bonded complexes of methane, ethylene, acetylene, and their derivatives with magnesium hydride were systematically investigated at MP2/aug-cc-PVTZ level. The results confirm that the strength of dihydrogen bonding increases in the following order of proton donors: C(sp³)-H<C(sp²)-H<C(sp)-H and chlorine substituents enhance the C-H×××H interaction. In the majority of the complexes with a cyclic structure, the Mg-H proton-accepting bond is more sensitive to the surroundings than C-H proton-donating bond. The nature of the electrostatic interaction in these C-H×××H dihydrogen bonds was also unveiled by means of the atoms in molecules(AIM) analysis. The natural bond orbital(NBO) analysis suggests that the charge transfer in the cyclic complexes is characteristic of dual-channel. The direction of the net charge transfer in the cyclic complexes is contrary to that previously found in dihydrogen bonded systems.



Sorbent Concentration Effect on Adsorption of Methyl Orange on Chitosan Beads in Aqueous Solutions

GUO Yali, HOU Wanguo, LIANG Jiling, LIU Jianqiang

2014, 30(5):  837-843.  doi:10.1007/s40242-014-4042-x

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The adsorption of methyl orange(MO) on chitosan(CS) beads in aqueous solutions was investigated by a batch equilibration technique. Special emphasis was focused on the effect of sorbent concentration(c_s) on the adsorption equilibration of MO on CS beads. An obvious c_s-effect was observed in the adsorption equilibration, i.e., the adsorption amount(Γ) was declined with c_s increase. The classical Langmuir model adequately described the adsorption isotherm for each given c_s. However, it could not be used to predict the c_s-effect observed. The applicability of the Langmuir-SCA isotherm, a surface component activity(SCA) model equation, to fit the c_s-effect data was examined. In the SCA model, the activity coefficient of sorbent surface sites,ƒ_H2O^s,was assumed to be a function of c_s due to the deviation of a real adsorption system from an ideal one, arisen from sorbent particle-particle interactions in real systems. The results show that the Langmuir-SCA isotherm could accurately describe the c_s-effect observed under the studied conditions. Furthermore, the effects of temperature(t), pH, and electrolyte(NaNO₃) concentration(c_NaNO3) on ƒ_H2O^s were examined. The results show that ƒ_H2O^s clearly decreased with increasing t(20-35℃) and pH(5-8), but no obvious change in ƒ_H2O^s was observed as c_NaNO3 varied in a range 0.001-0.010 mol/L. These results give a better understanding of the c_s-effect.



Solid-liquid Equilibria in the Quaternary System Na⁺, K⁺//Br^-, B₄O₇^2--H₂O at 298 K

CUI Ruizhi, SANG Shihua, LIU Qingzhu, WANG Pan

2014, 30(5):  844-847.  doi:10.1007/s40242-014-4026-x

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According to the compositions of the underground gasfield brines in the west of Sichuan Basin, the solubilities and densities of the solid-liquid equilibria in the quaternary system Na⁺, K⁺//Br^-, B₄O₇^2--H₂O at 298 K were determined by the method of isothermal solution saturation. From the experimental data, the phase diagram, water content diagram and density-composition diagram were obtained. This quaternary system is of simple eutectic type, without double salt and solid solution. There are two invariant points, five univariant curves, four fields of crystallization in the system. The equilibrium solid phases are Na₂B₄O₇·10H₂O, K₂B₄O₇·4H₂O, NaBr·2H₂O and KBr. Na₂B₄O₇·10H₂O has a larger crystallization field, and NaBr·2H₂O has a smaller crystallization field. It is also found that bromide has the salting-out effect on borate in the quaternary system Na⁺, K⁺//Br^-, B₄O₇^2--H₂O at 298 K.



Pyrolysis Mechanism of Hemicellulose Monosaccharides in Different Catalytic Processes

WANG Shurong, RU Bin, LIN Haizhou, SUN Wuxing, YU Chunjiang, LUO Zhongyang

2014, 30(5):  848-854.  doi:10.1007/s40242-014-4019-9

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The pyrolysis behaviors of four different hemicellulose monosaccharides, namely, two pentoses(xylose and arabinose) and two hexoses(mannose and galactose) catalyzed by HZSM-5 were investigated. The effects of two different processes by which the catalyst comes into contact with the substrate, namely, mixed with monosaccharide(in-bed) or layered above monosaccharide(in situ), were compared. Evolution characteristics of typical pyrolytic products(H₂O, CO₂, acids, furans and aromatics) were achieved by thermogravimetry-Fourier transform infrared spectroscopy. The in-bed catalytic process significantly lowered the pyrolytic temperature and increased the production of furans and acids at a low temperature by enhancing dehydration, retro-aldol fragmentation and Grob fragmentation. During the in situ catalytic process, volatiles generated from monosaccharides passed through a catalyst bed and underwent further dehydration, decarboxylation, and decarbonylation, significantly lowering the yields of acids and furans. The yield of aromatics was enhanced, and the corresponding volatilization temperature was lowered, especially under the in-bed catalytic conditions. Pentoses entered into the zeolite pores more easily than hexoses did because of their smaller molecular size; thus, the in-bed catalytic process drastically affected pentose pyrolysis.



Synthesis of Chlorogenic Acid Imprinted Chromatographic Packing by Surface-initiated Atom Transfer Radical Polymerization and Its Application

NIU Yuling, MA Meihua, GONG Yanru, WANG Yue, GONG Bolin

2014, 30(5):  855-862.  doi:10.1007/s40242-014-4201-0

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A novel chromatographic packing of chlorogenic acid(CGA) molecularly imprinted polymer(MIP) based on the 5.0 μm silica was prepared by surface initiated atom transfer radical polymerization(SI-ATRP) with 4-vinylpyridine(4-VP) as functional monomer, ethyl glycol dimethacrylate(EDMA) as cross-linker in the mixture of methanol and water(7:3, volume ratio) under mild reaction conditions. The characteristics of CGA MIP were investigated by elemental analysis, thermogravimetric analysis(TGA), Fourier transform infrared spectrometry(FTIR) and atomic force microscopy(AFM). The effects of some chromatographic conditions such as mobile phase composition and temperature on the retention time were investigated. The adsorption capacity of the stationary phase for compounds was determined by frontal chromatographic technique. The results show that Freundlich isotherm fits the experimental adsorption isotherm data better than Langmuir model does. The relatively high heterogeneity index values regressed with the Freundlich isotherm suggest the formation of fairly homogeneous MIP. Thermodynamic data(ΔΔH and ΔΔS) obtained by van't Hoff plots reveal an entropy-controlled separation. The CGA MIP column was shown to be successful for the separation and purification of chlorogenic acid from the extract of Honeysuckle.



Amphiphilic ABC Triblock Terpolymer Templating for Mesoporous Silica

WANG Huan, YAO Yuan, HAN Lu, CHE Shun'ai

2014, 30(5):  863-867.  doi:10.1007/s40242-014-4122-y

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Self-assembled triblock terpolymers have attracted intense attention in recent years because of their abundant variety of assembly mesostructure. We reported the synthesis of mesoporous silica materials with the amphiphilic ABC triblock terpolymer polyethylene-poly(ethylene oxide)-polycaprolactone(PE-PEO-PCL) as a template and tetraethoxysilane(TEOS) as a silica source. Increasing the hydrophilic head group(PEO) led to the decrease of packing parameter g, which gave rise to the mesophase transformation from a cylindrical two-dimensional hexagonal P6mm structure to a cage-type face centered cubic closed-packing mesostructure. This new templating route provided a new insight into the template factor governed inorganic-organic self-assembly mesophases.



Synthesis and Property of Flame Retardant Epoxy Resins Modified with 2-(Diphenylphosphinyl)-1,4-benzenediol

TIAN Xiujuan, WANG Zhongwei, YU Qing, WU Qingyu, GAO Jun

2014, 30(5):  868-873.  doi:10.1007/s40242-014-4031-0

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2-(Diphenylphosphinyl)-1,4-benzenediol(DPO-HQ) was synthesized by the reaction of diphenylphosphine oxide(DPO) with 1,4-benzoquinone(BQ), and characterized by Fourier transform infrared(FTIR), and nuclear magnetic resonance(¹H NMR, ¹³C NMR, ³¹P NMR) spectrometries. The thermal stability of DPO-HQ was investigated by thermogravimetric analysis(TGA). Flame retardant epoxy resin was synthesized based on DPO-HQ. The thermal properties and burning performance of cured epoxy resins were measured by differential scanning calorimetry(DSC), thermogravimetric analysis(TGA), limited oxygen index(LOI) and vertical burning test(UL-94V). The morphologies of cured epoxy resins after combustion were investigated by scanning electron microscopy(SEM) and electron probe microanalysis(EPMA). Moreover, the thermal stability(both in air and in N₂) of DPO-HQ and its cured epoxy resin was compared with that of 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO-HQ) and its cured epoxy resin. The thermal stability of DPO-HQ is comparable with that of DOPO-HQ, while the thermal stability of cured epoxy resin based on DPO-HQ is better than that based on DOPO-HQ.



Synthesis and Characterization of Dinuclear Aluminum Complexes Bearing N,N-Dialkylaniline-amido Ligands and Its Catalytic Properties for Lactone Polymerization

HAN Yancheng, ZHU Guangyun, ZHANG Mengmeng, WANG Shuai, YAO Wei, GAO Aihong, LU Ping

2014, 30(5):  874-878.  doi:10.1007/s40242-014-3507-2

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Two ligands[ortho-C₆H₄NR₂(CH₂NH)]₂CH₂CH₂(3: R=Me; 4: R=Et) were prepared by the reduction of preligands[ortho-C₆H₄NR₂(CH=N)]₂CH₂CH₂(1: R=Me; 2: R=Et). These ligands reacted with AlMe₃ to afford the corresponding dinuclear aluminum complexes {AlMe₂[ortho-C₆H₄NR₂(CH₂N)]}₂CH₂CH₂(5: R=Me; 6: R=Et). All the compounds were characterized by ¹H and ¹³C nuclear magnetic resonance(NMR) spectroscopies and elemental analyses. The catalytic properties of the aluminum complexes towards the ring-opening polymerization of lactones were investigated in the presence of benzyl alcohol. All the polymerization reactions were proceeded in a controlled manner.