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10 October 2016, Volume 37 Issue 10

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Cover and Content of Chemical Journal of Chinese Universities Vol.37 No.10(2016)

2016, 37(10):  0-0. 

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Articles: Inorganic Chemistry

Synergetic Effect of NbH@h-BN on Dehydrogenation of LiB\begin{array}{c}{H_4}^{†}\end{array}

TU Guoping, HE Jianling, XIAO Xuezhang, CHEN Lixin, REN Qianjiang, DU Xiyong, LUO Minger

2016, 37(10):  1757-1762.  doi:10.7503/cjcu20160468

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NbH@h-BN was prepared by mechanically milling h-BN, NbCl₅ and LiH, and the samples were detected by X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), transmission electron microscopy(TEM) and energy dispersive spectrometry(EDS). The enhancement of NbH@h-BN on the dehydrogenation of LiBH₄ and its mechanism were investigated. The results showed that the onset dehydroge-nation temperature and the apparent activation energy(E_a) of LiBH₄ were reduced to 380 ℃ and 142.31 kJ/mol respectively after the addition of NbH@h-BN, and the dehydrogenation kinetics of LiBH₄ was improved significantly. These remarkable results are largely attributed to the nano NbH particles which were dispersed on the surface of h-BN stably.



Syntheses, Characterizations and Properties of Two Unusual (3,4,6) and (3,6)-Connected Polynuclear 3D Metal-organic Frameworks^†

ZHAO Lun, ZHAO Changjiang

2016, 37(10):  1763-1768.  doi:10.7503/cjcu20160343

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Two novel polynuclcar metal-organic frameworks, namely, {[Cu₃(BCPBA)₂(bpmp)(H₂O)]·2DMF}_n(1) and {Zn₃(BCPBA)₂(bip)}_n(2)[H₃BCPBA=3,5-bi(4-carboxy-phenoxy)benzoic acid, bpmp=1,4-bis(pyridin-4-ylmethl)piperazine, bip=1,3-bis(imidazolyl)propane], were synthesized under solvothermal/hydrotherinal conditions. Their structures were determined by single-crystal X-ray diffraction(XRD) analysis and further characterized by infrared spectrosopy(IR), elemental analysis, and thermogravimetric analysis(TGA). Compound 1 is constructed by BCPBA^3- ligand linking three [Cu₂(CO₂)₄] clusters to form a 3D framework with (4·8²)(8⁶)(4²·6⁸·8³·9·10) topology. The 3D framework displays a self-penetra-ting phenomenon. Compound 2 exhibits a 3D framework with (4²·6)₂(4⁴·6²·8⁸·10) topology constructed by trinuclear Zn(Ⅱ) SBUs.



Effects of Functional Groups in α-Amino Acids on Reversible Oxygenation Performance of Co(Ⅱ) Complexes^†

XUE Peng, WEI Yana, YUE Fan, ZHANG Yi, WANG Jide

2016, 37(10):  1769-1775.  doi:10.7503/cjcu20160298

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In this paper, we selected histidine-Co(Ⅱ) complex as the target for researching its good oxygenation performance, and obtained short peptide, pseudo peptide and histamine through masking —N\begin{array}{c}{H}_3^{+}\end{array}, replacing —O^- and removing —COO^-, respectively. The impacts of three functional groups in α-amino acids on the oxygenation performance of their Co(Ⅱ) complexes were investigated via UV-Vis spectrophotometry. The comparative study showed that in α-amino acids, the —N\begin{array}{c}{H}_3^{+}\end{array} group plays a decisive role in oxygenation properties, —COO^- group plays a key role in reversibility of oxygenation, and —O^- has little influence on absorbing oxygen of complexes. The mechanism of α-amino acid-Co(Ⅱ) complexes reversible absorbing and releasing O₂ are discussed on the basis of previous research results.



Phase Structures and Hydrogen Storage Properties of Mg₂Ni_1-xCo_x Alloys Prepared by Solid Solution Sintering^†

MA Yong, LI Xiangzhi, LI Yongtao, LIU Dongming, ZHANG Qing’an, SI Tingzhi

2016, 37(10):  1776-1783.  doi:10.7503/cjcu20160284

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Mg₂Ni_1-xCo_x (x=0.10, 0.15, 0.20) alloys were prepared by a novel method combining solid solution with sintering process. The effect of Co content on the phase structures and hydrogen storage properties were investigated by XRD and pressure-composition-temperature analyser. It was found that the alloys consisted of a Mg₂Ni-type major phase Mg₂(Ni, Co), minor Mg and a new phase MgNi₃Co. The Mg₂(Ni, Co) compounds displayed a reversible hydrogen storage process. After hydrogenation, the quaternary Mg₂Ni_0.9Co_0.1H₄-type hydride was formed with an enthalpy change of the hydrogen desorption(ΔH_d=63.9 kJ/mol H₂) approximate to the parent hydride HT-Mg₂NiH₄. The Mg₂Ni_1-xCo_x(x=0.10, 0.15, 0.20) alloys showed a superior desorption kinetics and the desorption process was mainly controlled by two-dimensional phase-boundary migration. For the Mg₂Ni_1-xCo_x (x=0.10, 0.15, 0.20) alloys, the activation energy of hydrogen desorption (E_a) decreased with the increase of Co content. As a result, the E_a value of the Mg₂Ni_0.8Co_0.2 alloy was significantly lowered to 54.0 kJ/mol.



Analytical Chemistry

Rhodamine-based Cell Permeable Fluoresecent Turn-on Probes for Cupric Ion^†

MI Xiaolong, JIAO Xiaojie, LIU Chang, HE Song, ZENG Xianshun

2016, 37(10):  1784-1791.  doi:10.7503/cjcu20160402

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Two rhodamine-based fluorescent turn-on probes L1 and L2 were designed and synthesized for the detection of Cu²⁺ ion. L1 and L2 exhibit high selectivity toward Cu²⁺ ion over a wide range of metal ions in MeCN/H₂O(volume ratio 1∶5). The detection limits of the probes are down to 10^-8 mol/L range. Moreover, L1 and L2 can function as excellent fluorescence probes for imaging of cellular Cu²⁺ by means of fluorescence microscopy.



Analysis of Oil Yield from Oil Shale Minerals Based on Near-infrared Spectroscopy with Least Squares Support Vector Machines^†

ZHANG Fudong, LIU Jie, WANG Zhihong

2016, 37(10):  1792-1798.  doi:10.7503/cjcu20160344

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In order to improve the prediction accuracy and precision of near-infrared(NIR) spectroscopy model for analyzing the oil yield from oil shale, sixty-four oil shale samples from the No.2 well drilling of Fuyu oil shale base were analyzed based on least squares support vector machines(LS-SVM) calibration models. The Principal component-mahalanobis distance(PCA-MD) method and the Monte-Carlo sampling-based detection of outliers(MCS) method were investigated as means of removing the outliers. The modeling methods of radial basis function-based LS-SVM, partial least squares(PLS) and back propagation neural network (BPANN) were compared. The results showed that, compared with PCA-MD, the prediction accuracy of PLS models based on MCS was improved by 28%. The samples after eliminating the outliers were divided into the calibration set with 44 samples and the prediction set with 14 samples using the Kennard Stone method. One hundred LS-SVM calibration models were established based on preprocessing method of second-derivative and autoscaling. The mean determination coefficient(R²) were more than 90% and higher than PLS and BPANN models, and the fluctuation of R² were less than BPANN models. Thus, LS-SVM regression with MCS method can improve the accuracy and precision of oil yield of oil shale modeling.



Optimization of Conditions of the Electrochemical Detection of Methamphetamine^†

ZHANG Xuena, ZHONG Xinwen, ZHONG Yan, LU Haiyan

2016, 37(10):  1799-1803.  doi:10.7503/cjcu20160139

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Electrochemical method was used to detect methamphetamine(MA) and the effects of different detection conditions, such as the scan speed, the initial concentration of MA, pH value, electrode processing temperature and disruptors, on the electrochemical detection of MA were investigated to find out the optimal conditions for the electrochemical detection of MA. The results show that with BDD thin film electrode as the working electrode and at a scan rate of 50—100 mV/s, initial concentration of lower than 100 mg/L, pH=7.0 and electrode processing temperature of 100 ℃, the detection rate of MA is the fastest with best results, and the disruptors have no obvious effect on the detection of MA.



Organic Chemistry

Selenium-catalyzed Carbonylation of 4-Aminopyridine with Nitro Aromatics to 4-Pyridinylureas^†

ZHANG Xiaopeng, LI Zhengwei, WANG Yan, NIU Xueli, ZHANG Guisheng

2016, 37(10):  1804-1808.  doi:10.7503/cjcu20160410

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A facile, economical and environment-friendly approach to 4-pyridinylureas was reported. With cheap and easily available nonmetal selenium as the catalyst, triethylamine as the cocatalyst, carbon monoxide instead of virulent phosgene as the carbonylation reagent, the target products could be obtained via selenium-catalyzed redox carbonylation of 4-aminopyridine with nitro aromatics by bubbling of CO. The optimal reaction conditions were obtained by exploring the effects of main factors on the carbonylation reaction such as reaction temperature, reaction time, kinds of solvents and bases. Under the optimal conditions, 4-pyridinylureas could be obtained in moderate to good yields. The applicability of the substrates nitro aromatics was good. The possible reaction mechanism was also proposed at the end of this paper.



Physical Chemistry

Inclusion Mechanism of Cyclodextrins with Glutathione^†

SHEN Wen, SHAO Xueguang, CAI Wensheng

2016, 37(10):  1809-1816.  doi:10.7503/cjcu20160375

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By using molecular dynamics simulations combined with free energy calculations, the inclusion modes of α-, β-, and γ-cyclodextrins(CDs) with glutathione(GSH) in an aqueous environment were investigated at the atomic level. The free-energy changes for the six possible inclusion processes of the three types of CDs with GSH were calculated. The results show that the inclusion complex formed by GSH and α-CD with the orientation that the glutamic acid(Glu) residue entering from the secondary rim of the CD is the most energetically favored, wherein the methylene chain of the Glu is completely buried in the cavity of α-CD, and three hydrogen bonds are formed between α-CD and GSH. It is worth noting that in this most stable complex structure, the sulfhydryl group of GSH is included at the secondary rim, thereby being protected by α-CD. Moreover, hydrophobic and hydrogen-bonding interactions constitute the main driving force responsible for the formation of the host-guest complex. The favorable inclusion mode of GSH with β-CD is similar to that with α-CD, but the corresponding complex of the former is less stable than that of the latter. On the contrary, for γ-CD, the favorable orientation is that the Glu residue enters the cavity from the primary side of the CD. From the free-energy calculations reported herein, the relative binding affinity with GSH follows the ranking order α-CD>β-CD>γ-CD.



Study of Eight Membered Ring Zeolitic Catalyst of Cu/SAPO-35 over NH₃-SCR^†

LIU Ning, WANG Jiqiong, CHEN Biaohua, LI Yingxia, ZHANG Runduo

2016, 37(10):  1817-1825.  doi:10.7503/cjcu20160360

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A new type of SAPO-35 zeolite was synthesized utilizing hexamethyleneimine(HMI) as template. It was found that the acidity of SAPO-35 firstly increased and then decreased along with the increasing of SiO₂/Al₂O₃ molar ratio(0.3, 0.5, 0.7). With the molar ratio of SiO₂/Al₂O₃ = 0.7, the SM3 substitution mode occurred for the atomic Si during the SAPO-35 synthesis process, which could decrease the related acidity. The impregnation and wet ion exchange(WIE) method were applied to produce Cu modified SAPO-35 samples of Cu/SAPO-35, which were further evaluated in NH₃-SCR reaction system. According to various characterization results of XRF, NH₃-TPD, and H₂-TPR, it was revealed that the cationic Cu²⁺ constituted the main copper species on WIE method prepared Cu/SAPO-35, which displayed much better NH₃-SCR catalytic performance with respect to that of Cu/SAPO-35 prepared by impregnation method. Finally, various Cu/SAPO-35 with different SiO₂/Al₂O₃ molar ratio(0.3, 0.5, 0.7) were prepared by WIE and further evaluated for NH₃-SCR, wherein the influences of the acidities of parent SAPO-35 were thereafter investigated. It was revealed that the higher acidity of parent SAPO-15 could produce higher amount of exchanged Cu²⁺ cations, which resulted in superior NH₃-SCR activity and N₂ selectivity.



Preparation of Reduced-graphene-oxide/Au Composite Microelectrode Array and Its Optical and Electrical Characteristics^†

JI Jinhai, WEN Xuemei, CHEN Yang, BI Yangang

2016, 37(10):  1826-1832.  doi:10.7503/cjcu20160352

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The reduced-graphene-oxide/Au(R-GO/Au) composite microelectrode array was fabricated by a simple method. The graphene oxide(GO) array was prepared by two beam interference-holographic lithography technique, and then reduced by hydrazine vapor to partially remove the oxygen-containing groups. Ultrathin Au film was deposited on the reduced-graphene-oxide(R-GO) array to improve its conductivity. The results indicate that R-GO/Au composite microelectrode array exhibits excellent surface morphology with precisely controlled period and high resolution, good transparency in visible light region and high conductivity. The organic photovoltaic device based on the R-GO/Au composite microelectrode array exhibits a high power conversion efficiency of 3.43%.



Synthesis and Photocatalytic Activity of Cr Doped TiO₂ Nanowires/Reduced Graphene Oxide Composites^†

ZHU Jielian, XIA Xiaofeng, ZHU Shanshan, LIU Xiang, LI Hexing

2016, 37(10):  1833-1839.  doi:10.7503/cjcu20160323

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Cr-doped TiO₂ nanowires/reduced graphene oxide composites(Cr-TiO₂NWs/RGO) were synthesized via alkaline hydrothermal method, in which commercial TiO₂ nanoparticles(P25) and graphene oxide(GO) were used as the precursors while Cr(NO₃)₃·9H₂O was used as the Cr source. Other samples, such as TiO₂ nanowires(TiO₂NWs), were prepared via the similar method. The obtained samples were characterized by X-ray diffraction(XRD), Fourier transform infrared spectroscopy(FTIR), Raman spectroscopy, X-ray photoelectron spectroscopy(XPS), scanning electron microscopy(SEM), transmission electron microscopy(TEM) and UV-Vis diffuse reflectance spectroscopy(UV-Vis DRS). The photocatalytic activities of the samples were evaluated by measuring the photodegradation of methylene blue(MB) under visible light irradiation. The results showed that the degradation rate of MB catalyzed by Cr-TiO₂NWs/RGO was 2.2 times that catalyzed by TiO₂NWs within 120 min, and the degradation speed of MB catalyzed by Cr-TiO₂NWs/RGO is 5.8 times that catalyzed by TiO₂NWs.



Theoretical Studies on the Structure Stability and Magnetic Properties of Sn_nSm(n=1—9) Clusters^†

SUN Lin, WANG Huaiqian, WU Meng, LI Huifang, LI Xiaoyi, DU Dan, SHA Rui

2016, 37(10):  1840-1848.  doi:10.7503/cjcu20160318

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The geometrical structures, relative stabilities, electronic properties and magnetism of tin clusters and bimetallic complexes of tin clusters with one samarium atom Sn_nSm(n=1—9) were investigated with the Saunders “Kick” global stochastic search technique combined with density functional theory(DFT) calculations at the B3LYP/SDD level of theory. The results are as follows: (1) Samarium atom usually located on the surface in the doped tin-based with one samarium atom clusters. And the ground-state structures of the Sn_nSm(n=1—9) clusters prefer to three-dimensional structure with higher symmetry; (2) after doping samarium atom in the Sn-based cluster, the cluster has the increase average binding energy which should owe to the fact that the bonding energy of Sn—Sm bond is higher than Sn—Sn bond and has the stronger interaction; (3) the doped Sn-based with one samarium atom cluster has large magnetic moments, and the contribution of magnetic moment almost comes from 4f electron orbit of the samarium atom, while the contribution of tin atoms is negligible. With the increase of cluster’s size, bimetallic complexes cluster has the special phenomenon that the total magnetic moment tends to be stable.



Theoretical Studies on the Regioselectivity and Stereoselectivity of the Olefin Polymerization Catalyzed by Bridged-metallocene Complexes^†

TANG Yanhui, WANG Zhidong

2016, 37(10):  1849-1855.  doi:10.7503/cjcu20160271

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The reaction selectivity of olefin polymerization catalyzed by three different bridged-metallocene complexes[Me₂SiN(Me₄Cp)TiCl₂, Me₂SiCpFluTiCl₂ and Me₂SiInd₂TiCl₂] were studied with density functional theory. The calculation results show that the ligand of the metalloence complex creates special stereo environment which leads to unique catalytic properties. There are two ways for olefin insertion, primary and secondary insertion, in the chain initiation and chain propagation steps of propylene polymerization catalyzed by bridged-metallocene catalyst. The calculation results suggest that bridged-metallocene catalysts show a preference of primary insertion way in chain initiation step of propylene polymerization, and we believe this regioselectivity is resulted from the rigid structure of catalyst. In the subsequent chain growth step, the catalysts start to show their stereoregularity, and the product of polymerization is atac-, syn-, iso-PP, respectively. By studying the interactions of the monomer, the ligand and the growing chain, we revealed the origin of the regioselectivity and stereospecificity of bridged-metallocene catalyst and provide theoretical support for design of tailor made metallocene catalyst.



Synthesis, Characterization and n-Hexane Adsorption Performance of ZIF-8^†

LIU Kefeng, REN Danni, SUN Hui, SHEN Benxian, LIU Jichang

2016, 37(10):  1856-1862.  doi:10.7503/cjcu20160263

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The zeolitic imidazolate framework ZIF-8 was synthesized through a solvothermal process employing methanol as the solvent, zinc nitrate hexahydrate and 2-methylimidazole as zinc source and organic ligand, respectively. The products were characterized by means of XRD, N₂ adsorption, TG-DSC and SEM. In addition, selective adsorption performance for n-hexane on ZIF-8 was investigated. It is indicated that synthesized ZIF-8 has the sodalite crystal structure and a high crystallinity. From the N₂ adsorption results, ZIF-8 product has a pore size range of 0.4—1.1 nm, BET specific surface area of 1836 m²/g and pore volume of 0.65 cm³/g. Both TG-DSC and high-temperature in situ XRD analyses suggest its excellent thermal stability. As the temperature increases from 283 to 313 K, the diffusion coefficient for n-hexane adsorption on ZIF-8 varies from 2.53×10^-12 to 8.88×10^-12 cm²/s and diffusion activation energy is evaluated to be 31.11 kJ/mol. At 308 K, the dynamic adsorption capacity and Thomas adsorption rate constant for n-hexane on ZIF-8 are 187.3 mg/g and 2.17×10^-3 mL·min^-1·mg^-1, respectively. As compared to 5A molecule sieve, ZIF-8 displays around 100% higher adsorption capacity and almost 70% faster diffusion rate.



Highly Efficient Synthesis of 1,2,3-Triazoles Catalyzed by Schiff Base Functionalized Chitosan-CuBr Catalyst^†

XIONG Xingquan, JIANG Yunbing, XIAO Shangyun, SHI Lin, SONG Sida

2016, 37(10):  1863-1869.  doi:10.7503/cjcu20160252

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Pyridine-2-carboxaldehyde-modified chitosan(PYCS) was prepared through a simple procedure using chitosan(CS) and pyridine-2-carboxaldehyde in ethanol solution. Subsequently, PYCS supported CuBr(PYCS-CuBr) was synthesized by the reaction of PYCS with CuBr in acetone at room temperature under N₂ atmosphere. The obtained catalyst was characterized by FTIR, TGA and XRD. TGA result showed that the catalyst had a good stability up to 200 ℃ and could meet the normal use. The catalytic performances were evaluated in one-pot multi-component copper(Ⅰ)-catalyzed azide-alkyne cycloaddition(CuAAC) reaction under microwave-assisted condition. PYCS-CuBr was found to exhibit obvious catalytic activity to rapidly produce 1,2,3-triazole compounds under the microwave irradiation(480 W) at 70 ℃. Furthermore, the catalyst could be easily recovered by simple filtration and recycled at least 4 cycles without obvious loss of catalytic activity. 1,2,3-triazoles can be exclusively generated on multi-gram scale.



Effect of the Ionic Liquids with Anion Tf₂N^- on the Whole Cell Catalytic Properties of Penicillium Purpurogenum Li-3 Strain^†

Zhang Xin, LI Yang, CAO Hong, Ouyang Qiaofeng, Zheng Lanlan, LI Chun

2016, 37(10):  1870-1875.  doi:10.7503/cjcu20160201

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Penicillium purpurogenum Li-3 cells properties of growth, metabolism, permeability of cell membrane and catalysis were studied in five ionic liquids composed with anion Tf₂N^- and five different ca-tions. The results showed that, the ionic liquids [Py₁₄]Tf₂N, [Bmim]Tf₂N, [BPy]Tf₂N and [P_6,4,4,4]Tf₂N had inhibitory effect on the growth of penicillium purpurogenum Li-3 while ionic liquid [N_1,4,4,4]Tf₂N had a promoting effect. Through metabolic activity determination of retention value(R) in ionic liquids, [P_6,4,4,4]Tf₂N and [N_1,4,4,4]Tf₂N showed relatively high biocompatibility to cells. At the same time, five ionic liquids on cell membrane permeability were improved effect. Whole-cell catalysis results displayed that [Py₁₄]Tf₂N was optimal ionic liquid. When the addition of [Py₁₄]Tf₂N was 25%, after 84 h, glycyrrhetinic acid monoglucuronide(GAMG) rate and glycyrrhizin acid(GL) conversion rate were as high as 95.38% and 99.84%. Therefore, the addition of [Py₁₄]Tf₂N, greatly promoted the formation of conversion and product. It showed that the effects of five kinds of ionic liquids on cells properties of growth and metabolism, cell membrane permeability and the whole cell catalytic activity were not only related to the anion Tf₂N^-, but also played an important role in the composition, structure and properties of the cations.



1D Ag@Co₃O₄ Nanocomposite Catalysts Derived from Bimetallic Coordination Polymers^†

ZHANG Jiajia, CUI Fang, SHAO Qing, XU Linxu, CUI Tieyu

2016, 37(10):  1876-1881.  doi:10.7503/cjcu20160199

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1D, magnetic Ag@Co₃O₄ nanocomposite catalysts were prepared using a synthesized precursor of bimetallic coordination polymers Co(MAA)₂/Ag(Ⅰ) nanoribbon. The structure of the obtained material was characterized by Fourier transform infrared spectroscopy(FTIR), proton nuclear magnetic resonance(¹H NMR), powder X-ray diffraction(XRD), scanning electron microscopy(SEM) and transmission electron microscope(TEM). The results suggested that both the Ag and Co₃O₄ nanocrystals distributed uniformly in the entire Ag@Co₃O₄ nanoribbon. Meanwhile, UV-Visible absorption spectrum(UV-Vis) was used to investigate the catalytic performance of Ag@Co₃O₄ nanocomposites towards the reduction of methyl blue(MB) dye by sodium borohydride(NaBH₄). The results show that the material has excellent catalytic activity, cyclic stability and magnetic separation ability.



Fabrication of Transparent Superhydrophobic Nano-arrays and Self-ejecting Behavior of Dew Drops^†

ZHANG Youfa, AN Lijia, HAO Jianxia, YU Xinquan, CHEN Feng

2016, 37(10):  1882-1890.  doi:10.7503/cjcu20160198

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Highly-oriented ZnO nanorod arrays on FTO were fabricated by chemical oxidation of ZnO seed layer deposited by a sol-gel method. We studied the influence and its mechanism of solution concentration for crystal seed layer and thereafter growth time for nanorods on the morphology of nano-arrays, and then further explained the change of wettability and transparency. By precisely controlling the fabrication of the nano-arrays, we obtained a superhydrophobic surface with 95% of average transmittance. Owing to densely growth of nanorod arrays, the surface was mainly covered by micro-drops with the diameter of ca.10 μm under steady condensation. Moreover, the tiny dew drops could self-eject during coalescence together and then easily detach from the surface. The measured results of number density, coverage and average diameter of the drops therefore kept constant, showing excellent performance of anti-condensation.



Polymer Chemistry

Preparation of High Hydrophilic Epoxy Resin and Its Treatment on Carbon Fiber Surface^†

WU Bo, ZHENG Guo, LIU Xuzhao, SUN Yu, LIU Huibing, ZHU Jiawen

2016, 37(10):  1891-1899.  doi:10.7503/cjcu20160459

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Adipic acid modified epoxy resin(AAEP) was elaborated with adipic acid and epoxy resin using triethylamine as the catalyst. To optimize the reaction conditions, the effects of synthetic parameters were investigated on the conversion rate of adipic acid and the epoxy value of AAEP. Fourier transform infrared(FTIR) and nuclear magnetic resonance(¹H NMR) were used to characterize the chemical structures of AAEP. Then, the AAEP was neutralized with KOH to obtain the hydrophilic potassium adipic acid modified epoxy resin(AAEPK), which can be employed as a treating agent for carbon fiber(CF) in order to improve the dispersion and adhesive effect of CFs in the resin matrix. The selected concentration and adsorption amount were 1.0% and 3.0 mg/g according to the evaluation of the AAEPK emulsion properties and the CFs dispersion. In addition, the surface morphology and groups of treated CFs were assessed by Field emission scanning electron microscope(FE-SEM) and X-ray photoelectron spectroscopy(XPS). The results indicate that AAEPK is evenly distributed on the CF surface, and the dispersion of CFs in the resin matrix is improved dramatically. Furthermore, the flexural strength of treated chopped CF composite and interlaminar shear strength(ILSS) of treated CF cloth composite were proved to increase by 168% and 113%, which evaluates that the primary actions of AAEPK improving the mechanical properties of CF/epoxy resin composite was the improvement of dispersion and interface adhesive effect between CFs and the matrix.



Preparation of a Functionalized Graphene and Its Role as Delivery Carrier for Anti-cancer Drug^†

LUO Zewei, WANG Yimin, LIU Kunping, WEI Fujing, LI Yu, DUAN Yixiang

2016, 37(10):  1900-1906.  doi:10.7503/cjcu20160430

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A novel composite of poly(sodium-p-styrenesulfonate) functionalized graphene nanosheets(PSS-GNS) was prepared through reducing graphene oxide(GO) with hydrazine hydrate as the reducing agent and poly(sodium-p-styrenesulfonate)(PSS) as the protective agent. Then, the properties of PSS-GNS were characterized using ultraviolet-visible spectrometer(UV-Vis), Fourier transform infrared spectrometer(FTIR), X-ray diffraction(XRD), Raman spectrometer, scanning electron microscope(SEM), transmission electron microscope(TEM) and atomic force microscope(AFM). The results reveal that PSS-GNS synthesized are in the form of water-soluble and randomly dispersible nanosheets. Furthermore, the absorption behavior of PSS-GNS for rhodamine 6G used as a model anticancer drug was investigated, which demonstrate that PSS-GNS have a high loading capacity of 2.77 mg/mg. Release profiles in vitro indicate that the release of R6G from PSS-GNS/R6G complexes is pH-dependent and slow-release. PSS-GNS also exhibits low cytotoxicity against cancer cells. PSS-GNS/R6G complexes were easily delivered into the cancer cells and sustained the slow release of R6G for a long time. In conclusion, PSS-GNS could be apromising carrier for anti-cancer drug delivery.



Synthesis and Characterization of Polyprrole Microcapcule Containing ZnCl₂ Solution^†

YAO Jian, WANG Jianping, WEI Yao, WANG Xuechen, LI Wei, ZHANG Xingxiang

2016, 37(10):  1907-1914.  doi:10.7503/cjcu20160400

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Conductive polymer microcapsules have become a new research highlight because of its properties of both conductivity and micro/nano structure. Polypyrrole microcapsules containing ZnCl₂ solution were chemically synthesized by in-situ polymerization method with water-in-oil emulsion as soft template, sodium dodecylbenzenesulfonate(DBSNa) and p-toluene sulphonic acid(TsOH) as dopants, benzoyl peroxide(BPO) as oxidant. Characterization results show that the polypyrrole microcapcules are regular core-shell structure when the concentration of ZnCl₂ is 20%(mass fraction), the mass fractions of DBSNa, TsOH, BPO to the monomer are 1.27%, 4.12%, 123.71%, respectively. And the microcapcules have a fullness and smooth surface and the particle size of about 50 μm. This study is expected to expand the application of water-soluble drugs and all-solid-state ion selective electrode.



Investigation on Synthesis of Bletilla Striata Polysaccharides Amphiphilic Polymer and Drug-loaded Delivery System^†

GUAN Qingxiang, ZHANG Guangyuan, SUN Dandan, SUN Shilin, SUN Cheng, LIU Xin, HAN Bing

2016, 37(10):  1915-1920.  doi:10.7503/cjcu20160342

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Stearic acid(SA)-modified Bletilla Striata polysaccharides(BSPS) amphiphilic copolymers(SA-BSPS) were prepared. Fourier transform infrared spectroscopy and ¹H nuclear magnetic resonance spectroscopy(¹H NMR) were used to describe SA-BSPS group. The substitued degree of the SA-BSPS group was determined by the peak area of ^lH NMR. Docetaxel-loaded SA-conjugated BSPS(DTX-SA-BSPS) copolymer micelles were formulated and characterized in terms of particle diameter, Zeta potential, drug loading capacity(LC) and encapsulation efficiency(EE). Further, the uptake of rhodamine B-labeled SA-BSPS copolymer micelles and antitumor activity in vitro on human liver cancer cell line (HepG2) were carried out. The results indicated that SA was successfully conjugated with BSPS and the substitued degree of the SA-BSPS group was 12.94%. DTX-SA-BSPS copolymer micelles had an average size of (97.01±3.17) nm with Zeta potential in the range of (-19.56±0.22) mV. The drug encapsulation and loading capacity were (81.11±0.18)% and (9.13±0.17)% respectively. The average cell line viability of blank SA-BSPS polymer micelles were (78.82±3.25)% at 0.5 μg/mL after 72 h incubation. Fluorescent intensity of HepG2 cells incubated for 4 h with rhodamine B-labeled SA-BSPS copolymer micelles was higher than that of rhodamine B and fluorescent intensity exhibited an increase trend when incubation time were prolonged.



Preparation of Chiral 3-Aminophenol-formaldehyde Resin Nanofibers Using the Self-assemblies of Tetrapeptides as Template^†

CAO Yanfang, SHAO Changzhen, LI Baozong, LI Yi, YANG Yonggang

2016, 37(10):  1921-1925.  doi:10.7503/cjcu20160286

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A pair of tetrapeptide enantiomers derived from alanine was prepared through a classic solid phase peptide synthesis method. Their gel-forming properties were investigated, and their self-assemblies in methanol were selected as the template to prepare 3-aminophenol-formaldehyde resins via a sol-gel process. The obtained resins products were single-handed helical nanofibers characterized by field-emission scanning electron microscopy and transmission electron microscopy. Meanwhile, their optical activities were disclosed by circular dichroism. The research results indicate that 3-aminophenol-formaldehyde resins exhibited chirality both at the nano level and at the molecular level. Chirality transferred from the self-assemblies to the resins successfully.



Thermosetting Polyimide Resins and Composites Derived from 2-Phenyl-4,4'-oxydianiline^†

FAN Weifeng, LIU Xiuju, YAN Jingling, MENG Xiangsheng, LIU Jingfeng, WANG Zhen

2016, 37(10):  1926-1931.  doi:10.7503/cjcu20160243

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A series of imide oligomers with a degree of polymerization of 1, 2 and 3 was synthesized via a conventional two-step procedure, using 2-phenyl-4,4'-oxydianiline(p-ODA) and isomeric oxydiphthalic anhydrides as the monomers, and 4-phenylethynyl phthalic anhydride(4-PEPA) as the end-capping reagent. These imide oligomers were fully characterized in terms of solubility, melt viscosity, and thermal properties of cured resins. The solubility of imide oligomers based on 2-phenyl-4,4'-oxydianiline were higher than 30% in common organic solvents, such as N,N-dimethylacetamide(DMAc), tetrahydrofuran(THF), and 1,4-dioxane. The minimum melt viscosities for these oligomers were lower than 10 Pa·s, which was indicative of their excellent processability. Furthermore, the cured resins possessed good thermal properties, with glass transition temperatures(T_g) and 5% weight loss temperatures(T_5%) being up to 300 and 545 ℃, respectively. These resins were then formulated into carbon-fiber-reinforced composites, and the composite properties were studied. Composite PIC-4,4'-ODPA-2 displayed the best mechanical properties at both ambient and elevated temperatures.



Shape-memory Properties and Molecular Mechanism of Poly(methyl methacrylate)/Star-shaped Poly(ethylene glycol) Semi-interpenetrating Polymer Network^†

LI Xingjian, WU Ruiqing, LAI Jingjuan, PAN Yi, ZHENG Zhaohui, DING Xiaobin

2016, 37(10):  1932-1938.  doi:10.7503/cjcu20160202

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Poly(methyl methacrylate)/star-shaped poly(ethylene glycol) semi-interpenetrating networks(PMMA/SEPG) with star-shaped structure were synthesized by non-covalent interactions. In order to confirm the effect of star polymer structure on the shape memory and mechanical properties, poly(methyl methacrylate)/line poly(ethylene glycol) semi-interpenetrating networks(PMMA/LPEG) were also synthesized. The effect of molecular weight of PEG in the PMMA network on thermal properties, mechanical properties, dynamic mechanical properties and shape memory properties containing shape fixed ratio, recovery ratio and recovery rate was studied. The results show that, the embedding of the star-shaped structure greatly improved shape recovery ratio and recovery rate of the PMMA/SPEG with excellent mechanical properties compared to PMMA/LPEG. The shape memory effect was explained according to the tube model proposed by Edwards, which was demonstrated by the stress relaxation characteristics of the materials.