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10 March 2017, Volume 38 Issue 3

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Cover and Content of Chemical Journal of Chinese Universities Vol.38 No.3(2017)

2017, 38(3):  0-0. 

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Articles: Inorganic Chemistry

Effects of Ag or Yb Doping on Thermoelectric Properties of Ca₃Co_3.9Cu_0.1\begin{array}{c}{O_{9-\delta }}^{†}\end{array}

YANG Tao, CHENG Tiexin, ZHOU Guangdong

2017, 38(3):  335-340.  doi:10.7503/cjcu20160871

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A series of ceramic materials Ca_3-xAg_xCo_3.9Cu_0.1O_9-δ(x=0.1, 0.15, 0.2, 0.3) and Ca_3-yYb_yCo_3.9Cu_0.1O_9-δ(y=0.05, 0.1, 0.2, 0.3) which worked from 300 K to 880 K with excellent thermoelectric properties was prepared via sol-gel and cold-pressing method. The XRD results and SEM images revealed that the prepared samples are uniform crystal particles with high purity. Ag⁺ and Yb³⁺ ions have replaced the position of Ca²⁺ ions and they are dissolved in the crystal, which changes the cell volume of the dual doping materials but does not change the crystal symmetric structure. The resistivity and Seebeck coefficient of the materials reveal that the concentration of the current carrier is optimized by dual doping, accordingly the resistivity decreases continuously and the value of Seebeck coefficient increases continuously with the increase of temperature. It can be concluded from the calculations that the effective mass of the electron contributes to the increase of Seebeck coefficient. The thermal conductivity of dual doped samples decreases with the increase of temperature, and the phonon thermal conductivity still contributes more in the prepared system, which is consistent with the results of single doped samples. The figure of merit ZT of Ca_2.7Ag_0.3Co_3.9Cu_0.1O_9-δ reaches 0.2 at 880 K.



Application in Electric Double Layer Capacitor of Porous Carbon Derived from Potassium Carbonate Activated Molasses^†

GAO Ye, PANG Liyun, CAO Liyuan, WANG Wei, GUO Yupeng, ZHAO Chun

2017, 38(3):  341-345.  doi:10.7503/cjcu20160817

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A facile method for the synthesis of porous carbon from molasses with K₂CO₃ as the activator(KPCs) was present. Effects of different conditions on the yield of KPCs were analyzed. The samples were characterized with scanning electron microscopy(SEM), X-ray diffraction(XRD), N₂ adsorption-desorption analysis and Fourier transform infrared spectroscopy(FTIR). The results show that the KPCs have graphitized layer stack structure, and have surface functional groups of hydroxyl, carboxyl, ester and ether group. Also, the KPCs have porous structure and their specific surface area is up to 1219 m²/g. The optimized activation temperature was 800 ℃. The porous carbon based molasses will be an ideal electric double layer capacitors material in the field of energy storage.



Preparation and Antibacterial Properties of Ag/Fe₃O₄/rGO Nanocomposite^†

DU Wenxiu, YANG Juan, SANG Yuxiang, ZHANG Lili, ZHAO Nan, XU Kai, CHENG Xiaonong

2017, 38(3):  346-354.  doi:10.7503/cjcu20160753

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Antibacterial sliver/ferroferric oxide/reduced graphene oxide(Ag/Fe₃O₄/rGO) nanocomposite with magnetic separation performance was prepared by in situ reduction method with FeCl₂·4H₂O and AgNO₃, using NaBH₄ as reducing agent and graphene oxide(GO) as the carrier. The nanocomposite was characterized by X-ray powder diffraction(XRPD), X-ray photoelectron spectroscopy(XPS) and transmission electron microscopy(TEM). The results showed that the Fe₃O₄ and Ag nanoparticles were uniformly distributed on the rGO sheets. Hysteresis loop test results indicated excellent magnetism of the nanocomposite, the saturation susceptibility(M_s) was 40.5 A·m²·kg^-1. Adsorption and settling of magnetic separation in the bacteria liquid could be completed within 10 min by adding Ag/Fe₃O₄/rGO in magnetic field. Selecting Escherichia coli(E. coli) and Staphylococcus aureus(S. aureus) as the experimental strains, the antibacterial properties of the composite was evaluated by the agar diffusion method, minimum inhibitory concentration(MIC) and minimum bactericidal concentration(MBC). Ag/Fe₃O₄/rGO showed strong antibacterial activities against E.coli and S.aureu. The antibacterial circle diameter was 18 mm and 13 mm, the MIC was 50 mg/L and 80 mg/L, and the MBC was 30 mg/L and 50 mg/L respectively.



Synthesis of Ordered Mesoporous TiN Powder via Ammonia Reduction Nitridation Reaction and Its Electrochemical Performance^†

NI Jie, WEI Hengyong, BU Jinglong, LIU Huixing, CUI Yi, LÜ Dongfeng, WEI Yingna, ZHANG Lifang

2017, 38(3):  355-361.  doi:10.7503/cjcu20160572

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The ordered mesoporous TiN powder was synthesized by reduction-nitridation method based on the nonhydrolytic sol-gel process using titanium tetrachloride as the raw material, P123 as the structure-directing agent and cyanamide as the stabilizer. The structural information of the composite powder was characterized by wide-angle/small-angle X-ray diffraction, scanning electronic microscopy, N₂ adsorption-desorption analysis, and the electrochemical properties were characterized by cyclic voltammetry(CV) and galvanostatic charge-discharge(GCD) measurements. The results show that the synthesized TiN powder was highly pure cubic TiN phase and had ordered mesoporous structure, its specific surface area was 97 m²/g. The CV curves at different scan rates look like the rectangle. The specific capacitance was 233 F/g at current density of 50 mA/g, and remained 90% even after 2000 cycles. When the power density was 0.1 kW/kg, the energy density was as high as 65 W·h/kg.



Analytical Chemistry

Detection of Pharmaceuticals by Nitrogen Direct Analysis in Real Time Mass Spectrometry^†

SHI Xiaoyu, SU Rui, YANG Hongmei, LIAN Wenhui, WAN Xilin, LIU Shuying

2017, 38(3):  362-368.  doi:10.7503/cjcu20160645

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Direct analysis in real time-mass spectrometry(DART-MS) was usually employed as a novel method for fast screening of target compounds in complex matrix samples. However, nitrogen direct analysis in real time(N₂-DART) mass spectrometry(MS) analysis of labile compounds usually tends to be challenging because of its low ionization energy and complex background signals. In the current study, N₂-DART ion source coupled with high resolution Orbitrap MS based on a make-up solvent approach, which was designed for analysis of pharmaceuticals sensitively and easily, was reported. The main parameters of ion source, including gas temperature, gas type, scan mode, and solvent effect, were studied. The results confirmed that, compared with conventional He-DART, N₂-DART could generate obviously different ions in positive ion mode. And the sensitivity obtained by N₂-DART was found to be comparable with that obtained by He-DART. Typical mechanisms including the reactions of oxidation and rearrangement in N₂-DART were also discussed in detail. For the purpose of further confirmation, theoretical calculation was employed to verify the feasibility of the rearrangement reaction. The results demonstrated that N₂-DART-MS could provide a rapid and reliable method for the identification of active ingredients in pharmaceuticals, and may be applicable to other mixtures.



Detection of Chemical Additives in Food Using Raman Chemical Imaging System^†

ZHAI Chen, PENG Yankun, LI Yongyu, ZHAO Juan

2017, 38(3):  369-375.  doi:10.7503/cjcu20160640

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Raman chemical imaging applies the advantages of Raman spectroscopy to an imaging approach for screening large samples, allowing the presence and distribution of adulterants within a food material to be visualised. The potential of Raman chemical imaging technology for simultaneously detecting benzoyl peroxide(BPO) and L-ascorbic acid(LAA) in wheat flour powder was investigated. A line-scan Raman imaging system consists of a 785 nm laser, a fiber optic probe, a dispersive imaging spectrometer, a spectroscopic CCD camera, and a two-axis positioning table. This system acquired hyperspectral images in the effective spectral range of 0 to 2885.7 cm^-1. BPO and LAA were mixed into wheat flour powder in the concentration range of 0.1%—30% for each adulterant. The quantitative models were established to predict the content of BPO and LAA in wheat flour. The average spectrum of region of interest was used as Raman signal of the sample. The intensity of the Raman signal depends on the BPO and LAA content of wheat flour. The peak intensity of BPO at 1001, 1777 cm^-1 and LAA at 630, 1656 cm^-1 can be used for monitoring the additive levels. Linear regression models were established with the correlation coefficient(R²) of 0.9828 and 0.9912 for BPO and LAA, respectively. The adaptive iteratively reweighted Penalized Least Squares(airPLS) correction method can remove fluorescence background signals from the wheat flour powder. Single-band corrected images at unique Raman peaks identified for BPO and LAA can be used to create images for each adulterant using a simple thresholding method. The binary images of the two adulterants can be combined to create chemical images including both BPO and LAA, in which identification, spatial distribution, and morphological features of the two adulterant particles can be visualized in the background of the wheat flour powder. The high-throughput Raman chemical imaging method can be extended to authenticate other powdered foods and ingredients adulterated with Raman-active chemicals.



Surface Enhanced Raman Spectroscopic Investigation of PAHs at a PDMS-Au Composite Substrate^†

CHEN Hui, XIA Di, YUAN Yaxian, XU Minmin, YAO Jianlin

2017, 38(3):  376-382.  doi:10.7503/cjcu20160553

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A composite surface enhanced Raman spectroscopy(SERS) substrate was fabricated through the spin coating of polydimethylsiloxane(PDMS) layer onto the Au nanoparticles monolayer film(Au MLF). This substrate exhibited the high uniformity with the derivation of SERS intensities less than 10%. Four kinds of PAHs(naphthalene, naphthalene, phenanthrene and pyrene) were employed as probe molecules to verify the performance of the composite SERS substrate. The results showed that the limit of detection(LOD) of naphthalene, anthracene, phenanthrene and pyrene detected by PDMS-Au composite substrate were 10^-6, 10^-7, 10^-8 and 10^-7 mol/L, respectively. By comparing to Au MLF substrate, the LODs were decreased by almost one order of magnitude. It was mainly originated from the physical enrichment of target molecules by the PDMS layers. Moreover, this approach opens a potential application in the identification of the mixture of PAHs.



Preparation of MoS₂ Hollow Nanospheres and Application in Ultrasensitive Electrochemical Biosensing Platform for Micro-RNA Detection^†

LIU Renzhi, LI Xiaoyan

2017, 38(3):  383-391.  doi:10.7503/cjcu20160488

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Molybdenum disulfide hollow sphere nanomaterial was synthesized through template-assisted method, the morphological structure was characterized by scanning electron microscopy(SEM), X-ray diffraction(XRD) and Raman spectroscopy. A novel microRNA electrochemical biosensor was constructed by immobilizing of aptamer on the electrode that was modified with Au nanoparticles and MoS₂. The electrochemical behavior of the modified electrode was tested by cyclic voltammograms, differential pulse voltammetric and electrochemical impedance. The results indicate that the as-prepared biosensor shows a good linear relationship between the current variation and logarithm of the miRNA concentration ranging from 1.0×10^-10 mol/L to 1.0×10^-16 mol/L. The detection limit was estimated to be 0.055×10^-16 mol/L. The constructed sensor shows good selectivity, high sensitivity, strong stability characteristics and has a broad application prospect.



Organic Chemistry

yntheses and Anti-cholinesterase Activity of 4-N-Phenylaminoquinoline Derivatives ^†

LIU Yuming, TIAN Lijun, HU Dong, NIE Jianbing

2017, 38(3):  392-397.  doi:10.7503/cjcu20160880

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A series of 4-N-Phenylaminoquinoline derivatives was designed and synthesized, and their anti-cholinesterase activities were evaluated using Ellman assay. The results demonstrated that the stretched-out quaternary pyridine in quinoline ring greatly improved the cholinesterase inhibition of target compounds. Compound 16 exhibited the most potent inhibitory activities against both acetylcholinesterase(AChE) and butyrylcholinesterase(BChE) from the prepared series, with IC₅₀ values of 0.92 and 14.20 μmol/L, respectively, which showed superior activitities compared with the reference drug galanthamine. These results suggest that compound 16 may be valuable as a new parent compound for further structural modifications.



Synthesis of Sialidase Detection Agent(X-Neu5Ac)^†

LEI Xiong, ZHU Chenhui, GUO Hongyao, WANG Xiaojing, HU Weiyue, WANG Feng, LI Wenhong

2017, 38(3):  398-402.  doi:10.7503/cjcu20160811

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The sialic acid methyl ester was synthesized via the methanol esterification of sialic acid under the catalysis of concentrated sulfuric acid, and yield increased by 20% compared with all previously reported literatures. In the following acid chloride reaction, the yield of compound 4 increased from 86.4% to 98.9%. Compound 4 was condensed with compound 6 in the presence of sodium hydride in tetrahydrofuran(THF) and then was hydrolyzed by MeONa to obtain the target product(X-Neu5Ac). The process adopted the catalytic method of concentrated sulfuric acid to get compound 2. The results indicate that the accessible raw material and safe operation avoided the use of expensive resin and the exist of dangerous diazomethane. Meanwhile, the one-pot method in acid chloride reaction benefited the reaction of acetyl protection and chlorination. As the key intermediate, the synthesis condition of compound 7 was optimized by single factor experiment to obtain the optimal reaction condition: the reaction temperature of 25 ℃, reaction concentration of 200 mL solvent per 10 g substrate, the reaction time of 10 h. By detecting the active ingredient in X-Neu5Ac, the stability and color sensitivity of products met relevant requirement and its structural properties were characterized by means of ¹H NMR, ESI-MS and HPLC-MS.



Synthesis and Crystal Structure of Trans-3-phenyl-12-substituted Cyclododecanone^†

YANG Mingyan, ZHANG Li, WANG Daoquan, WANG Ming an

2017, 38(3):  403-412.  doi:10.7503/cjcu20160717

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2-Cyclododecenone was prepared via oxidation of cyclododecanone with o-iodylbenzoic acid(IBX), then 3-phenyl cyclododecanone was synthesized by 2-cyclododecenone and phenyl boronic acid under catalysis of palladium acetate. A series of 3-phenyl-12-substitutedcyclododecanone was regioselectively prepared by the reaction of 3-phenylcyclododecanone with different reagents, and their structures were characterized by ¹H NMR, ¹³C NMR and HR-MS. The crystals for four compounds were obtained in the solution and X-ray diffraction analyses were carried out. The results showed that [3333]-2-one conformation was took by the cyclododecanone ring of 3-phenyl-12-substituted cyclododecanone with trans-configuration of two substituted groups. One case was that the two substituted groups were at the same side, phenyl was at β-corner-anti position of the carbon atom in one side of carbonyl, and the other groups were at α-corner-syn position of the carbon atom in the other side of carbonyl in their crystals. The other case was that the two substituted groups were at the different sides, both phenyl and the other groups were at side-exo position of the carbon atoms in two sides of carbonyl in their crystals. The results of quantum mechanics calculation were consistent with those of X-ray diffraction.



Asymmetric Synthesis and Antibacterial Activity of Chiral 2-Methoxycarbonyl-4-fluorophenyl-1,5-benzothiazepines^†

MU Boshuai, CHANG Suna, BIAN Yanqing, LI Yuan

2017, 38(3):  413-420.  doi:10.7503/cjcu20160546

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The synthetic route was confirmed via the study of introduction or removing chiral auxiliary (R)-4-phenyl-2-oxazolidinone and optimizing reaction conditions. Eighteen optically active 1,5-benzothiazepines were synthesized under the chiral induction of (S)/(R)-4-benzyl-2-oxazolidinone and characterized by ¹H NMR, ¹³C NMR, IR and HRMS. The relative configuration of compound 9h was validated by X-ray diffraction analysis. The e.e. values of the products were analyzed by HPLC. The antifungal activities of compounds were screened using the disk diffusion method against C. neoformans. The compounds which were synthesized with S-4-benzyl-2-oxazolidinone had high antibacterial effects against C. Neoformans. By contrast, the compounds which were synthesized with R-4-benzyl-2-oxazolidinone and racemic compounds had lower antibacterial effects. Moreover, The MIC and MFC values of the highly biological compounds 14a—14f were lower than those of fluconazole.



Synthesis and Biological Activities of Novel Cyanoacrylate Derivatives Carrying 5-Arylisoxazole Group^†

SHI Yujun, FANG Yuan, LI Yang, CHEN Jia, LI Gang, WANG Qingmin, DAI Hong

2017, 38(3):  421-428.  doi:10.7503/cjcu20160510

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In order to find novel cyanoacrylate derivatives with potent biological activities, fourteen new cyanoacrylates bearing a 5-arylisoxazole moiety were synthesized by multistep synthetic procedures with two key intermediates 5 and 6. The intermediate 5 was synthesized from methyl 5-arylisoxazolyl-3-carboxylate via reduction, chlorination, condensation, and hydrazine cleavage. The structures of target compounds 7 were confirmed by ¹H NMR, ¹³C NMR and elemental analysis. The bioassay data showed that some target compounds exhibited good herbicidal activities at the dosage of 1500 g/ha. In postemergence treatment, compounds 7h, 7i, and 7m had 90%, 40%, and 100% herbicidal activity against Brassica juncea at 1500 g/ha, compounds 7m and 7n showed 100% and 80% herbicidal activity against Stellaria media at 1500 g/ha, compounds 7m and 7n displayed 100% and 85% inhibitory rates against Chenopodium serotinum L. at 1500 g/ha. In addition, some of the title compounds had satisfactory anti-tumor activities. Compounds 7b and 7c showed wonderful inhibitory activities against HepG2 cells with the IC₅₀ values of 3.2 and 10.1 μmol/L, respectively.



Physical Chemistry

Catalytic Effect of n(H₂O)(n=1,2) on the Reaction of HO₂+NOHNO₃ ^†

WANG Rui, LI Yili, FENG Xukai, SONG Liang, ZHANG Tianlei, WANG Zhuqing, JIN Lingxia, ZHANG Qiang, XU Qiong, WANG Zhiyin

2017, 38(3):  429-441.  doi:10.7503/cjcu20160775

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The mechanism and rate constant for the HO₂+NOHNO₃ reaction, without and with n(H₂O)(n=1,2) was investigated at the CCSD(T)/aug-cc-pVTZ//B3LYP/6-311+G(2df,2p) level. The results show that, incorporation of the catalyst[n(H₂O)(n=1,2)] into the reaction of HO₂+NOHNO₃, the reactions between NO radical and HO₂…(H₂O)_n(n=1,2) complexes are more favorable than the corresponding reactions of HO₂ radical with NO…(H₂O)_n(n=1,2) complexes, as well as the reactions of HO₂…H₂O+NO…H₂O, H₂O…HO₂+NO…H₂O and H₂O…HO₂+ON…H₂O due to the lower barrier of the former reactions and the larger rate constant of the reaction between HO₂…(H₂O)_n(n=1,2) complexes and NO. Meanwhile, the catalytic effect of n(H₂O)(n=1,2) is mainly taken from the contribution of a single water vapor, due to the effective rate constant of H₂O…HO₂+NO reaction was larger by 10—12 orders of magnitude than that of NO+HO₂…(H₂O)₂ reaction. Compared with the reaction of HO₂+NOHNO₃ without water molecule, the single water molecule in H₂O…HO₂+NO reaction has a positive influence on enhancing the rate of HNO₃ formation, and the catalytic effect increase with the temperature increase. At 298.2 K, water vapor shows the most significant catalytic effect with the value of k'_RW1/k_total up to 67.93%, indicating that the single water molecule in H₂O…HO₂+NO channel shows a positive catalytic effect on enhancing the rate of HNO₃ formation under atmospheric conditions.



Influence of Interaction with Cucurbit[7]uril on Solubility, Stability and Antioxidant Activity of 2'-Hydroxychalcone^†

LI Mengjie, LIAN Xiaowei, XU Zhiling, XING Xuyang, ZHANG Jianxin, LI Rui, TAO Zhu, ZHANG Qianjun

2017, 38(3):  442-447.  doi:10.7503/cjcu20160733

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The host-guest interactions and properties of 2'-hydroxychalcone(CET) with cucurbit[7]uril(Q[7]) were investigated by means of ¹H NMR, IR, UV-Vis absorption and fluorometry spectroscopy. The results revealed that 2'-hydroxychalcone could form an inclusion complex of 1∶1 with Q[7]. The inclusion constants of CET with Q[7] obtained by UV absorption and fluorescence spectroscopy were 1.0248×10⁶ and 1.253×10⁶, respectively. The phase-solubility experiments revealed that the solubility of CET increased 52 times by interacting with Q[7][c(Q[7])=1×10^-3 mol/L]. The time-scaled UV absorption spectra showed that Q[7] increases the stability of CET by 3.5 times. The antioxidant activity(ABTS method) of both the CET@Q[7] inclusion complex and CET proved to be good scavenging effect to the ABTS radical, IC₅₀ values were 3.4×10^-5 and 2.4×10^-5 mol/L, respectively. Thus, Q[7] could not only increase the solubility and stability of CET, but also have little effect on the antioxidant activity of CET. As a result, stability and water solubility were obviously improved.



Excited State Intramolecular Proton Transfer of Salicylaldehyde Derivatives and Its Application in Fluorescent Probe Field^†

LI Xueying, CHEN Yanming, CUI Na, ZHANG Wanyu, WANG Zhiming

2017, 38(3):  448-455.  doi:10.7503/cjcu20160680

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According to the electronic structure control theory, the electron withdrawing substituent was introduced to the para-positon of phenol hydroxyl group to stable the ketone conformation, and the target compound, 2-hydroxy-5-(4-cyanophenyl)-benzaldehyde(CN-SA), was prepared. Series of spectral tests show that, CN-SA not only shows the typical excited state intramolecular proton transfer(ESIPT) fluorescence characteristics, but also significantly increases the ketone distribution proportion in radiation transition process, so that the fluorescence intensity and color change visibly. CN-SA not only exhibites selective recognition for the external solvent environment, but also has specific response and quantitative analysis ability for aggregation process(aggregation effect) and the hydrogen bond formation ability following environmental changes(pH effect and anions effect). With little structure tuning, CN-SA could realize alcohol and ketone conformation distribution changes and can be used as a simple multiple stimulation-responsive fluorescence probe.



Fabrication of Superhydrophobic Film of Co(OH)₂CO₃ Nanowires and Its Anticorrosion^†

SHI Yanlong, FENG Xiaojuan, WANG Suiqian, FENG Chunchun

2017, 38(3):  456-463.  doi:10.7503/cjcu20160633

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Superhydrophobic film of Co(OH)₂CO₃ nanowires was fabricated on nickel foils by hydrothermal method. The film exhibits superhydrophobicity after being modified by dodecanthiol(DDT), water contact angle and water gliding angle on the surface is 152.3° and 5°, respectively. The results reveal that the synergistic effects of hierarchical structures with micro/nanometer scale combining with low surface energy material induced the formation of superhydrophobicity. Compared with pristine nickel foil and unmodified Co(OH)₂CO₃ nanowires film, the film modified with DDT performs preferable properties of anticorrosion. The researches are expected to provide a reference for the fabrication of superhydrophobic metal surface and investigations of its properties of anticorrosion.



In Situ Crystallized Zirconium Phenylphosphonate Films on the Copper Mesh and Its Application in Oil/water Separation^†

LI Qintao, SUN Wen, ZHANG Qin, PAN Huifen, XU Jie

2017, 38(3):  464-470.  doi:10.7503/cjcu20160575

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In situ crystallized zirconium phenylphosphonate films on the copper mesh using hydrothermal method have superhydrophobic and superhydrophobic properties due to benzene ring being arranged in the outermost layer of zirconium phenyl phosphonate and its micro-nano roughened structure. This material can selectively filter oil from oil/water mixtures without any low-surface-energy material modification. The crystallized zirconium phenylphosphonate films on copper mesh have both mechanical stability and chemical stability. In addition to separation of oil/water mixtures, the copper mesh with ZrPP crystallization are capable of separating surfactant-free oil-in-water and water-in-oil emulsion efficiently, which can be a candidate to be applied in the actual production process.



Promoting Effect of Nonmetal Ion Doping and Hierarchically 3D Dendrimeric Architecture for Visible-light-active Mesoporous TiO₂ Photocatalyst^†

ZHANG Chunlei, HUANG Danya, SUN Minghui, OUYANG Yiting, WANG Chao, LI Xiaoyun, CHEN Lihua, SU Baolian

2017, 38(3):  471-478.  doi:10.7503/cjcu20160573

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This study aimed at getting insight into the promoting effect of nonmetal ion(N and C) doping and hierarchically 3D dendrimeric architecture on mesoporous TiO₂ based photocatalysts for efficient visible light activated photocatalysis. A comparison of the photocatalytic efficiencies of bare and nonmetal ion doped mesoporous TiO₂ with/without-hierarchically 3D dendrimeric architectures was studied. The resultant photocatalytic performance of TiO₂ based samples was improved greatly by nonmetal doping treatment. Meanwhile, the mesoporous TiO₂ based materials with hierarchically 3D dendrimeric architecture present superior photocatalytic activity compared to the one without hierarchical structure.



Colloidal Magnetically Assembled Photonic Crystals and Ionic Strength Sensing^†

YOU Aimei, CAO Yuhua, CAO Guangqun

2017, 38(3):  479-483.  doi:10.7503/cjcu20160486

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Magnetic composite nanoparticles(MCNPs) with magnetic core and polymers shell were prepared via miniemulsion polymerization technique. As the assembling blocks, MCNPs were constructed into colloidal magnetically assembled photonic crystals(CMA-PCs) with the assistance of a magnetic field. The characterization results of TEM and SEM show that MCNPs have uniform spherical morphology, a distinct core-shell structure and good monodispersity. The average diameter of MCNPs was 112 nm, the shell of MCNPs was about 10 nm in thickness. The diffraction color of CMA-PCs changed from orange to purple, the reflection wavelength shifted from 607 nm to 434 nm as the ionic strength increased from 0.03 mmol/L to 0.75 mmol/L, with response time less than 10 s. As a chemical sensor, CMA-PCs have the advantages of convenient, sensitive and naked eye visual detection, and could be applied in the semi-quantitative detection of ionic strength.



Polymer Chemistry

Preparation, Characterisation and Electrochromic Properties of Copolymer Films Based on 3,4-Ethylenedioxythiophene and Pyrrole-3-Carboxylic Acid

LV Yaokang, LIU Youyou, PAN Yun, LIU Gang, CHEN Jun, GUO Yun, CHU Wenjing, SHEN Lian, ZHANG Cheng

2017, 38(3):  484-494.  doi:10.7503/cjcu20160829

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Four new copolymers P(EDOT:P3C)-1, P(EDOT:P3C)-3, P(EDOT:P3C)-5, P(EDOT:P3C)-10 were prepared via electrochemical co-polymerization using different molar ratios(1:1, 3:1, 5:1, 10:1) of 3,4-ethylenedioxythiophene(EDOT) and pyrrole-3-carboxylic acid(P3C). The prepared four copolymers have good electrochromic properties, high electrochemical activity and good transmittance. Compared with poly(3,4-ethylenedioxythiophene)(PEDOT), the prepared copolymers have more abundant color change. P(EDOT:P3C)-1 has mainly four colors under different potentials, namely, dark red, pale brown, grey blue and blue. P(EDOT:P3C)-3 and P(EDOT:P3C)-5 possess the color change of purple, light purple and blue. P(EDOT:P3C)-10 can be dark purple, light purple and blue under different potentials. In addition, we also prepared a copolymer P(EDOT:P3C)-1-Ti based on EDOT, P3C and polyoxotitanate cluster[Ti₇(OEt)₁₉O₅(CoBr)]. This film not only exhibits typical electrochromic properties but also has the ability of electric-catalytic oxidation of water.



Easy Synthesis of Porous Polyurea and Its Application in Enzyme Immobilization and Kinetic Resolution of Racemic Phenylethanol^†

ZHOU Yamei, KONG Xiangzheng, HAN Hui, JIANG Xubao, ZHU Xiaoli

2017, 38(3):  495-502.  doi:10.7503/cjcu20160827

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Porous polyurea(PPU) was prepared through one step precipitation polymerization in a mixed solvent of water-acetone with toluene diisocyanate(TDI) as the only monomer through step polymerization of TDI with its amine derivatives in-situ produced by TDI reaction with water. The morphology, pore size and size distribution of the PPU were characterized by scanning electron microscope and mercury intrusion. The results demonstrate that PPU is of irregular and granular form with the size of the granules varied from 30 μm to 50 μm. PPU is featured by a continuous pore size distribution from 2 nm to 100 μm with two main regions of pore size distribution, one from 2 nm to 100 nm and another from 5 μm to 100 μm. Amine groups on PPU surface are converted to aldehyde via a treatment with glutaraldehyde, followed by immobilization of lipase from pseudomonas fluorescens(PFL) onto the surface of activated PPU by covalent bonding of the aldehyde groups with the primary amine of the enzyme. Impact of GA and PFL concentration in the process was studied. It is found that the optimized results are obtained when PPU is activated by GA at pH=8 with a concentration of 0.17 mol/L followed by PFL immobilization with PFL concentration of 2.56 mg/mL. Under the optimized conditions, a maximal PFL immobilization of 95.2 mg/g was observed with a high activity of the immobilized PFL of 375 U/mg and the relative activity of 76% relative to free PFL. The immobilized PFL is then used as the catalyst in the kinetic resolution of 1-phenylethanol, the reactivity and the enantioselectivity compared with the free PFL. The results reveal that the activity and the enantioselectivity of the immobilized PFL are greatly enhanced in comparison with the free enzyme. The kinetic resolution of the racemic PEOH is achieved with pure enantiomers. Therefore, this PPU material prepared through simple precipitation is a good potential candidate for enzyme immobilization, the immobilized enzyme is efficient for kinetic resolution of racemic molecules.



Preparation of Gold Nanoparticles Loaded Hollow Silica Spheres and Their Catalytic Performance^†

MENG Qingnan, WANG Kai, TANG Yufei, ZHAO Kang, XIANG Siyuan, ZHANG Kai, ZHAO Lang

2017, 38(3):  503-508.  doi:10.7503/cjcu20160807

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A natural polymer of Arabic gum was chosen as the reducing and stabilizing agent to synthesize Au nanoparticles. The Arabic gum and Au nanoparticles(AG-Au) hybrid colloids were obtained by dropping the mixture of the Au nanoparticles, Arabic gum molecules and ammonia solution into ethanol. Tetraethyl orthosilicate(TEOS) was added into the system to form a silica layer on the as-prepared AG-Au hybrid colloids. Finally, the Au loaded silica(Au@SiO₂) hollow particles were produced by simply water washing. For the Au@SiO₂ hollow particles characterization, transmission electron microscope(TEM), X-ray diffraction(XRD) and N₂ adsorption-desorption measurement were conducted. The Arabic gum serves as the templating agent during the formation process of the Au@SiO₂ hollow particles, which has been proved by control experiments. The as-prepared Au@SiO₂ hollow particles show good performance and stability in the catalytic reaction of reduction of methylene blue(MB) with NaBH₄.