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    10 September 2020, Volume 41 Issue 9
    Content
    Cover and Content of Chemical Journal of Chinese Universities Vol.41 No.9(2020)
    2020, 41(9):  1-0. 
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    Review
    Photocatalytic Application of Covalent Organic Frameworks
    LI Li, LI Pengfei, WANG Bo
    2020, 41(9):  1917-1932.  doi:10.7503/cjcu20200409
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    Covalent organic frameworks(COFs) are crystalline porous organic materials, which are built from organic building blocks through covalent bonds. COFs have the characteristics of well-defined pore structure and high specific surface area. COFs have been widely used in gas storage and separation, catalysis, sensing, energy storage, photoelectric conversion and many other fields. Introducing organic building blocks with adjustable light absorption into COFs provide COF with a great potential in photocatalysis. In recent years, COFs have developed rapidly in the field of photocatalysis. This paper summarizes the recent progress of COFs in the fields of photocatalytic hydrogen production, photocatalytic carbon dioxide reduction, photocatalytic organic reactions, and photocatalytic degradation of pollutants, and looks forward to its further prospects in the field of photocatalysis.

    Recent Progress of Fluorescent Nanoprobes for Organelle pH Detection
    GONG Shaohua, ZHANG Xia, LI Na, TANG Bo
    2020, 41(9):  1933-1944.  doi:10.7503/cjcu20200279
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    pH homeostasis plays a significant role in maintaining the normal functions of different organelles in living cells. The disruption of pH homeostasis will result in the disorder of organelle function and further lead to the relevant diseases, such as cancer, neurodegenerative disease, etc. Therefore, it is important to quantitively detect pH and monitor the fluctuation of organelle pH in living cells to explore the pathology of relevant diseases. Fluorescent probes are suitable for pH detection in living cell based on the advantages of noninvasive and high spatiotemporal resolution imaging. In this review, we summarized the recently developed fluorescent nanoprobes for the pH detection of different organelles. The chances and challenges of the practical application of fluorescent nanoprobes were also discussed.

    Electrochemiluminescence of Quantum Dots: Research Progress and Future Perspectives
    CAO Zhiyuan, SUN Hui, SU Bin
    2020, 41(9):  1945-1955.  doi:10.7503/cjcu20200390
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    Electrochemiluminescence(ECL) has become one of the most advanced immunodiagnostic method due to its near-zero background and high sensitivity. Ruthenium(Ⅱ) tris(bipyridine)[Ru(bpy)32+] and its derivatives have been applied in commercial diagnostics, but their optical properties can not meet the requirement of state-of-art ECL analysis. Quantum dots(QDs) possess outstanding luminescence properties and seem to be ideal for developing a new generation of ECL emitters. However, the mechanism of ECL generation from QDs deserves further in-depth investigations and the ECL performance of QDs also needs to be improved. In this review, we focus on the important advancements and key scientific issues of QDs ECL. After an overview of the developments of the field, future perspectives about the developments of QDs ECL are also exhibited. We believe that spectroscopy, synthesis chemistry and electrochemistry should be combined together to advance the research.

    Recent Advances in the Synthesis of Multi-Mechanophore Polymers
    DENG Yakui, YUAN Yuan, CHEN Yulan
    2020, 41(9):  1956-1967.  doi:10.7503/cjcu20200310
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    The design and synthesis of multi-mechanophore polymers(MMPs) have provided great opportunities for observing, quantifying, and exploiting mechanochemical transformations, and thus promoted the development of polymer mechanochemistry. In this contribution, we make an overview of representative synthetic methodologies for MMPs, including post-polymerization modification, step-growth polymerization, ring-opening metathesis polymerization, and living/controlled radical polymerization. The characteristics, advantages and applicable systems of these methods are discussed, respectively. The aim of this review is to open a new avenue towards the synthesis and applications of diverse mechano-responsive polymers and materials.

    Article
    Near Infrared Spectroscopy for Low-temperature Water Structure Analysis
    ZHAO Hongtao, SUN Yan, GUO Yichang, CAI Wensheng, SHAO Xueguang
    2020, 41(9):  1968-1974.  doi:10.7503/cjcu20200401
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    The structure of water and its flexibility have been widely studied due to the mysterious behavior in biological and chemical process. Under supercooled conditions, water may have special properties, such as the thermodynamic response and phase transformation. In this study, water structure in dimethyl sulfoxide(DMSO)-water mixture at low temperature was studied by near infrared spectroscopy combined with Raman spectroscopy and molecular dynamics simulation for understanding the mechanism of DMSO in reducing the freezing point of water. Through the analysis of the near-infrared and Raman spectra of the mixtures with diffe- rent DMSO contents, the spectral feature reflecting the interaction of DMSO and water was found, and two hydrogen-bonded DMSO-water structures(DW2 and D2W) were determined in the mixture of different DMSO/ water ratio. Analyzing the spectra obtained by temperature-dependent near-infrared spectroscopy for a 30%DMSO-water mixture over the temperature range from 20 oC to -70 oC, it was found that DW2 structure inhibits the formation of tetrahedral water structure at low temperature and this founding can be used to explain the reason for DMSO reducing the freezing point of the mixture. The result of molecular dynamics simulation also gave a proof for the reliability of the conclusion.

    Inorganic Chemistry
    Electrochromic Composite Film and Device Based on Vanadium Tungstate and Congo Red
    YANG Yanyan, ZHANG Jie, FENG Suyang, QI Yue, LIU Xiaoqing, YU Xiaoyang, QU Xiaoshu
    2020, 41(9):  1975-1982.  doi:10.7503/cjcu20200299
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    The [PEI/P2W15V3/PEI/CR]20 film containing [P2W15V3O62]8? anions, Congo red anions and poly- ethyleneimine cations was fabricated by layer-by-layer self-assembly technology through electrostatic attraction, and the [PEI/P2W15V3]20 film was also prepared by a similar method. The morphology and electrochromic properties of the films were studied by means of SEM, UV-Vis and electrochemical workstation. The results show that the composite film can realize the cyclic color change from light red to bluish violet and then to light red, and the electrochromic properties of [P2W15V3O62]8? anions were well maintained. The light contrast of the film is 22.55%, the coloring efficiency can reach 122.67 cm2/C, the transmittance(in 500 nm) loss of the composite film is only 6.94% after 400 cycles, and its stability is good. The electrochromic device also realizes the color modulation from light red to bluish violet. This research will provide a reference for solving the problem of single color change of polyoxometalate electrochromic materials.

    Analytical Chemistry
    Absolute Quantification of Haemoglobin in Whole Blood by Species-unspecific Isotope-dilution Liquid Chromatography-inductively Coupled Plasma Mass Spectrometry
    PAN Mengyun, FENG Liuxing, LI Hongmei
    2020, 41(9):  1983-1988.  doi:10.7503/cjcu20200321
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    A methodology based on isotope dilution-high performance liquid chromatography(HPLC) coupled with inductively coupled plasma mass spectrometry(HPLC-ID-ICP-MS) was established for the absolute quantification of haemoglobin(HGB) in whole blood by measuring content of iron, through two specific methods. The first method is online HPLC-ID-ICP-MS quantitative technology, following the separation of HGB by HPLC, the enriched 54Fe isotope solution was continuously mixed with the eluate from HPLC via a three-way connection. The isotope ratio of 56Fe/54Fe was measured online by ICP-MS. The concentration of HGB was calculated by isotope dilution equation by the contents of iron in each protein. For Tf in the whole blood, we changed the flow rate of isotopically enriched 54Fe spike online to simultaneous quantification of HGB and Tf on the basis of complete chromatographic separation. In the other method, the total Fe concentration was first measured by bulk ID-ICP-MS after digesting the whole blood sample. And then the ratio of Fe content from HGB in blood obtained by peak area after HPLC separation, which achieved accurate quantification of HGB. The quantification results obtained with the two methods are (115.3±2.4) mg/g and (115.5±2.1) mg/g, respectively, which are in good agreement and the RSDs are all within 3%. The methods can be used as the main reference method to quantify HGB in clinic. All the proposed methods were validated for the analysis of a human blood certified reference material(IRMM/IFCC-467), and it might be used as the main reference method for HGB quantitative analysis in clinical.

    Construction of High Efficiency Uric Acid Sensor Based on the co-Crystal Enhanced Electrochemiluminescence from 9,10-Diphenylanthracene-perylene Microcrystals
    LIAO Ni, ZHANG Jieyuan, HUANG Ziyang, ZHAO Yanxi, CHAI Yaqin, YUAN Ruo, ZHUO Ying
    2020, 41(9):  1989-1995.  doi:10.7503/cjcu20200294
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    A new luminophore with co-crystal enhanced electrochemiluminescence(ECL) was obtained by the surfactant assisted self-assembly of the non-coplanar molecule 9,10-diphenylanthracene(DPA) and planar molecule perylene(Pe). The introduction of DPA in the co-crystals can not only reduce the aggregation-caused quenching(ACQ) effect of perylene, making the ECL emission of Pe molecule from the dimer or multimer excited state(1Pe2*) to the monomer excited state(1Pe*), but also plays a role as a donor molecule, providing effective energy transfer to the acceptor molecule of Pe, which further enhances the ECL response. The electrochemical sensor for uric acid based on DPA-Pe microcrystals has an extremely wide linear of 0.01 μmol/L—5.0 mmol/L and a detection limit of 4.0 nmol/L. In addition, the sensor has a nice stability and selectivity for uric acid detection.

    Synthesis of a β-Ketoenamine-linked Chiral Covalent Organic Framework and Its Application in Capillary Gas Chromatography
    YAN Yilun, HUANG Xiaoling, FAN Jun, CAI Songliang, ZHENG Shengrun, ZHANG Weiguang
    2020, 41(9):  1996-2002.  doi:10.7503/cjcu20200206
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    A new β-ketoenamine-linked chiral covalent organic framework(COF), namely TfpMth COF, was prepared by the reaction of 1,3,5-triformylphloroglucinol(Tfp) with (S)-2,5-bis(2-methylbutoxy)terephthalohydrazide(Mth). The obtained TfpMth COF powder was characterized by various techniques such as powder X-ray diffraction analysis, Fourier transform infrared spectrometer(FTIR), thermogravimetric analysis(TGA), nitrogen adsorption-desorption measurement and so on, indicating its virtue of good crystallinity, high porosity, and excellent thermostability. Thus, we used TfpMth COF as a new stationary phase to prepare the TfpMth COF-bound capillary column by an in situ growth method. A series of linear and branched alkanes and alcohols, as well as mixtures of benzene and cyclohexane, ethylbenzene and styrene can be separated using the TfpMth-bound capillary column. This result provides a new idea for the application of β-ketoenamine-linked COF in chromatographic separation, and also gives a reference for the study of novel gas chromatographic stationary phases.

    Mechanism of Photocatalytic Degradation of Rhodamine B by TiO2 Nanowire Array with Internal Extraction Electrospray Ionization Mass Spectrometry
    LI Xiaoqian, ZHANG Hua, LU Haijian, LIU Chang, LIU Qinglong, MA Xiayu, FANG Yuanping, LIANG Dapeng
    2020, 41(9):  2003-2010.  doi:10.7503/cjcu20200165
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    By means of hydrothermal synthesis, the TiO2 nanowire array was prepared on the SnO2 conductive glass(FTO) substrate doped with F, and it was combined with the internal extraction electrospray ionization mass spectrometry(iEESI-MS) to realize the detection of Rhodamine B intermediate product and the conjecture of its reaction mechanism. The effects of ion source voltage, ion transmission tube temperature and eluting agent on the signal strength of rhodamine B and its degradation products were systematically investigated. The results showed that the optimum Rhodamine B intermediate product and its degradation product signal could be obtained under the condition that the photocatalytic reaction time was 2 h, the reaction solution volume was 15 μL, the ion source voltage was 3 kV, the ion transmission tube temperature was 300 ℃, and the eluting agent was 0.5% methanol-acetic acid(volume ratio). Under the optimized conditions, 8 kinds of intermediate products were detected from Rhodamine B reaction solution, and the degradation mechanism of rhodamine B was inferred. In this method, the detection limit(S/N≥3) of rhodamine B quantitative analysis is 0.1 μg/L, and the relative standard deviation(RSD, n=6) is 2.1%—7.3%, which shows that this method has the characteristics of low testing limit, high sensitivity, less sample consumption during detection, fast analysis speed and simple operation. In addition, this method can also be used to detect the intermediate products of other photocatalytic reactions, widen the application of mass spectrometry in the field of environment, and provide new ideas for the future exploration of the degradation mechanism of environmental pollutants.

    Rapid Classification of Daphniamagna and Daphnia pulex by Surface-coated Probe Nanoelectrospray Ionization Mass Spectrometry Lipidomics
    DENG Jiewei, YANG Yunyun, LIN Li, LUAN Tiangang
    2020, 41(9):  2011-2017.  doi:10.7503/cjcu20200154
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    A surface-coated probe nanoelectrospray mass spectrometry(SCP-nanoESI-MS) based lipidomics method was developed for the rapid species identification of Daphnia genus. A microscale surface-coated probe was used to extract and enrich the lipids from Daphnia, and the lipids enriched on the probe were then analyzed by nanoelectrospray ionization mass spectrometry under ambient and open-air conditions. Structural identification of the lipid species was achieved via high resolution MS analysis. By using the proposed method, the lipidomics fingerprints of D. magna and D. pulex were obtained, and the characteristics of lipid compositions from D. magna and D. pulex were also investigated. Rapid classification of D. magna and D. pulex as well as the identification of lipid markers were achieved via chemometrics. The results showed that the proposed SCP-nanoESI-MS lipidomics method has the advantages of fast analysis speed and high sensitivity, and can be used for rapid identification of Daphnia species.

    Physical Chemistry
    Spectroscopic Characterization of Solvation Effect for a Polarity-Sensitive BDP
    ZHAO Yuhui, LI Mingle, LONG Saran, FAN Jiangli, PENG Xiaojun
    2020, 41(9):  2018-2024.  doi:10.7503/cjcu20200339
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    Polarity is an important physical and chemical property of solvent systems. Hence it is of a great significance to study the dynamics mechanism of excited photosensitizers influenced by the solvent polarity. A push-pull molecule BDP, which contains dipyrrometheneboron difluoride(BDPIPY) and carbazole groups, was synthesized. Measurements such as steady-state spectra, fluorescence lifetime and femtosecond/nano- second transient absorption were performed on BDP in different polar solvents in order to research spectrosco- pic characters of its excited states. The red-shifted fluorescence spectra with increasing solvent polarity show that it is possible to form an intramolecular charge transfer(ICT) state in excited BDP. Furthermore, fluorescence lifetimes measured by means of time-correlated single photon counting(TCSPC) also prove the existence of ICT state since the fluorescence lifetime of BDP in high-polar solvent is shorter than that in low-polar solvent. Femtosecond transient absorption experiments reveal that a solvation-stabilized relaxed ICT state(ICT′) is formed only in high-polar solvent because of its solvation effect. The time constant of solvation-stabilized process is 3.14 ps obtained by global analysis of the transient absorption spectra based on the sequential model. In addition, nanosecond transient absorption measurements show different lifetimes of the first excited triplet state(T1 state) for BDP in high/low-polar solvent under air or N2 condition. The lifetime of T1 state in low-polar solvent with oxygen is much shorter than that without oxygen, indicating the generation of singlet oxygen by energy transfer. However, there is only a small difference between the lifetimes of T1 state in high-polar solvent with or without oxygen, which indicates that it is difficult to generate singlet oxygen by energy transfer. This result proves that the energy of T1 state in high-polar solvent becomes lower accordingly, which will cause a lower singlet oxygen yield because of the disadvantage in energy transfer. The following DPBF experiment confirms the result above, BDP in low-polar solvent can generate more singlet oxygen than in high-polar solvent. This study provides an effective method for the design of molecular structures and the investigation of polarity effect of photosensitizers.

    Support Effect of Nanosized Hierarchical Silicalite-1 Zeolite on the Properties of Ziegler-Natta Catalyzed Polypropylene
    HUANG Pai, ZHOU Guangyuan, LIU Bo, WANG Lei, ZHANG Jiaqi
    2020, 41(9):  2025-2031.  doi:10.7503/cjcu20200331
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    Due to the characteristics of special pore structure, large specific surface area, excellent stability and unique shape selectivity, zeolites inorganic porous material has become excellent green inorganic supports. Herein, nanosized hierarchical silicalite-1(S-1) zeolite with MFI topology was used as the inorganic support for Ziegler-Natta catalyst. The physicochemical properties of nanosized S-1 support were characterized in detail by X-ray diffraction(XRD), scanning electron microscopy, nitrogen adsorption-desorption, and other characterization methods. The effects of S-1 support on properties of polypropylene were also studied. In propy- lene polymerization, the larger specific surface area and hierarchical characteristics of the nanozied inorganic support S-1 are beneficial to increase the loading of Ziegler-Natta and improve the diffusion of reactants and products. Besides, the S-1 support can serve as a morphology-directed template, thus exhibiting a replica effect on the polypropylene product. Likewise, the crystallinity and isotactic index of the polymer products are improved in the propylene polymerization reaction at the same pressure and reaction temperature, due to the shape-selective effect and the replica effect of the hierarchical S-1 inorganic support. Consequentially, the S-1 support is conducive to improving the melting point of polypropylene products.

    Preparation and Electrical Properties of Germanium Telluride Field Effect Transistor
    ZHANG Xin, ZHAO Fulai, WANG Yu, LIANG Xuejing, FENG Yiyu, FENG Wei
    2020, 41(9):  2032-2037.  doi:10.7503/cjcu20200311
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    Compared with three-dimensional(3D) materials, two-dimensional(2D) materials have excellent photoelectric properties, and can be used in many fields such as electronics and photocatalysis, etc. Two-dimensional germanium telluride(2D-GeTe) belongs to a narrow-band gap semiconductor, and its carrier mobility has a theoretical value of up to 1066.33 cm2·V-1·s-1, but its crystal structure limits its application in the field of optoelectronics. In this work, a GeTe alloy was synthesized by a high-temperature sintering method in a tube furnace, and then a GeTe nanosheet with a lateral dimension about 10 μm successfully was prepared by micromechanical exfoliation. After heat-treating the material, through the method of electron beam exposure and vacuum sputtering coating, using titanium(10 nm)/gold(60 nm) alloy as the contact electrode, the 2D-GeTe based field effect transistor(FET) was prepared, and the electrical properties were measured at room temperature. The results show that the GeTe nanomaterials obtained by exfoliating have good crystallinity, a wide optical absorption range, and an optical band gap of 1.98 eV, which belongs to p-type semiconductors. At the same time, the FET devices prepared based on 2D-GeTe exhibits favorable electrical properties, with a channel length of 7 μm, a channel width of 3 μm, and a carrier mobility of 6.4 cm2·V-1·s-1, the switching current ratio is 670. And the output curve is non-linear, which indicates that due to the preparation process and the environment, there is a clear Schottky barrier between the material and the contact electrode. In short, the study of 2D-GeTe electrical properties and the successful preparation of FET devices have enriched the types of two-dimensional materials in the field of semiconductor optoelectronic devices, and provide some reference and guidance for the research of high optoelectronic devices.

    Effect of Particle Aggregates on the Surface Properties of Amphiphilic SiO2 Particles in Anhydrous Foam
    LI Gen, WANG Keliang, LU Chunjing
    2020, 41(9):  2038-2045.  doi:10.7503/cjcu20200296
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    Two types of Janus particles with different relative amphiphilic areas for the preparation of non-aqueous foam were synthesized. In addition, particles with uniformly modified surfaces were synthesized as contrasts. By adjusting the properties of the oil mixture, the behavior of the particles on the oil and gas surface was measured and compared, and the role of the particle agglomerates in particles adsorption was studied. Affected by the contact angle of the particle surface, the surface activity of Janus particles is not always greater than that of the uniformly modified particles, which is reflected in the surface tension reduction ability and the volume of foam generated. The particles are not adsorbed from the bulk phase to the surface in the form of mutually independent particles, but in the state of particle agglomerates. And the contact angle of the Cassie-Baxter composite surface requiring particle agglomeration is around 90°, while the intrinsic contact angle of the particles is less than 70.1°.

    Theoretical Study on the Nature and Cooperation of CH•••O and CH•••π Interactions in the Pillar[5]arene and n⁃Alkanes Complexes
    SUN Tao, WANG Yibo
    2020, 41(9):  2046-2053.  doi:10.7503/cjcu20200291
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    Using the calculation result of the binding energy of the CCSD(T)/CBS method as the standard, the CAM-B3LYP-D3BJ/def2-SVPD density functional theory(DFT) method was chosed to calculate the bin- ding energy of the MeP5…CnH2n+2(n=1—10, 12, 14, 16) complexes. The results show that there is a strong interaction between the host and guest, and the binding energy increases with the growth of the alkane carbon chain. The Gibbs free energy and enthalpy change are both less than zero at standard conditions(nominally 298.15 K, 101325 Pa), which indicating that the formation of the complexes is spontaneous, and the main driving force associated with is enthalpy. The nature and cooperation of the C―H…π and C―H…O interactions between alkanes and dimethoxypillar[5]arene(MeP5) were explored using the absolutely localized molecular orbitals energy decomposition analysis(ALMO-EDA) method, and found that the sum of the electrostatic and dispersion effects accounts for about 94% of the total attraction, and their contribution is similar, with polarization and charge transfer accounting for only 6%.

    Interactions Between Polybrominated Diphenyl Ethers and Human Serum Albumin Using SPR and Molecular Docking
    ZHANG Aiqin, WANG Man, SHEN Gangyi, JIN Jun
    2020, 41(9):  2054-2060.  doi:10.7503/cjcu20200270
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    The interactions between eight polybrominated diphenyl ethers(PBDEs) and human serum albumin(HSA) were studied by using surface plasmon resonance(SPR) and molecular docking technologies. The results of SPR kinetic analysis showed that both the number and substitution position of bromine on PBDEs had regular influences on the interaction. Bromine atoms mainly affected the dissociation rate of interaction, cau- sing the affinity of PBDE and HSA to increase with the number of bromine atoms. The position of bromine on PBDEs mainly affected the association rate of interaction, resulting in the high affinity of m-substituted PBDE and HSA than that of o-substituted PBDE in isomers. The results of molecular docking indicated although all PBDEs were mainly bound to site I of HSA, the difference of amino acid residues around the binding site affected the binding ability. The van der Waals force and hydrogen bond force had greater contribution to binding free energy than electrostatic force. The experimental datum of SPR were in good agreement with the results of computer simulation.

    Surface Properties of Ce1-xMnxO2 Catalyst on the Catalytic Activities for Direct Synthesis of DMC from CO2 and Methanol
    ZHANG Guoqiang, SUN Yuchen, SHI Yabo, ZHENG Huayan, LI Zhong, SHANGGUAN Ju, LIU Shoujun, SHI Pengzheng
    2020, 41(9):  2061-2069.  doi:10.7503/cjcu20200250
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    A series of Ce1-xMnxO2 catalysts with different Mn doping amounts were prepared by coprecipitation method and applied to catalyze direct synthesis of dimethyl carbonate(DMC) from CO2 and methanol. The effects of surface properties of Ce1-xMnxO2 on the direct synthesis of DMC from CO2 and methanol were studied by means of X-ray diffraction(XRD), N2 adsorption-desorption, transmission electron microscopy(TEM), X-ray photoelectron spectroscopy(XPS) and programmed temperature desorption(TPD). The results indicated that Mn ions successfully entered into the lattice of CeO2 and formed a uniform solid solution. With the increase of Mn doping, the number of weak acid and base sites on the catalyst surface decreased gradually, while the number of medium and strong acid and base sites increased. Meanwhile, the oxygen vacancy content on the catalyst surface increased first and then decreased with the increase of Mn doping. When the doping of Mn was low, the ratio of Mn2+ on the catalyst surface was high, which was beneficial for the reaction of Ce4++ Mn2+→Ce3++ Mn3+ and the formation of oxygen vacancies. With further increase of Mn doping, the ratio of Mn4+ on the catalyst surface increase, which was conducive to the reaction of Ce3++Mn4+→Ce4++Mn3+, resulting in the decrease of oxygen vacancy. The catalytic activity of Ce1-xMnxO2 catalyst was linearly correlated with the content of oxygen vacancy on surface.

    Polymer Chemistry
    Synthesis and Properties of Imidazolium-based Polyethylene Ionomer
    ZHANG Jun, WANG Bin, PAN Li, MA Zhe, LI Yuesheng
    2020, 41(9):  2070-2077.  doi:10.7503/cjcu20200322
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    The novel ethylene/5-iodomethyl norbornene(IMNB) copolymers with high molecular weight, narrow molecular weight distribution and different incorporation of comonomer were firstly synthesized by using titanium catalysts bearing two β-ketiminato chelate ligands, then iodine atoms distributed randomly along the copolymer chains were subsequently converted into ionic groups via nucleophilic substitution reaction with N-methylimidazole, followed by exchanging the I- counteranions with CH3SO3-, CF3SO3-, or Tf2N-. Thus, a series of imidazolium-based polyethylene ionomers bearing different counteranions were readily obtained. As observed, the introduction of ionic groups destroyed the crystallization of copolymers, contribu-ting to the decrease of melting temperature and crystallinity. Such effect became more significant with increasing the ion content. Ionomers had higher glass transition temperature(Tg) than that of ethylene/IMNB copolymer, suggesting the interaction between ionic groups restricted the mobility of surrounding segments. Compared with copolymer, polyethylene ionomers exhibited better thermal stability, hydrophilic property and tensile strength. With the same ion content, the stress-at-break values of the ionomers followed the order: CH3SO3- >CF3SO3- >Tf2N-, whereas the strain-at-break values in the opposite order.

    Preparation and Properties of Polyvinye Alconol/Polyvinylpyrrolidone/Iodine Composite Hydrogels
    GONG Yuning, WANG Qi, WANG Honglei, GUAN Shuang
    2020, 41(9):  2078-2084.  doi:10.7503/cjcu20200245
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    A low-temperature freezing method was used to prepare a PVA/PVP-I composite hydrogel with adjustable mechanical properties by changing the ratio of PVA and iodophor(PVP-I), the freezing time, and the number of freeze-thaw cycles. The mechanical properties, microstructure, iodine release and bacteriostatic property of the composite gel were characterized. The results show that the controllable mechanical properties of the PVA/PVP-I composite hydrogel can meet the demand for wound dressing; the network structure of the composite hydrogel can effectively reduce the decomposition rate of iodine under ultraviolet rays, and achieve sustainable release of iodine, thereby exerting antibacterial properties, broadening the scope of application of iodine disinfectants.

    Preparation of Large-sized Microencapsulated Phase Change Materials Through Pickering Emulsion Stabilized by Monodisperse Polymer Microspheres
    LI Boxin, YANG Junge, YIN Dezhong, GAO Chengqian, ZHANG Qiuyu
    2020, 41(9):  2085-2089.  doi:10.7503/cjcu20200235
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    Monodispersive poly(glycidyl methacrylate)(PGMA) microspheres were prepared by dispersive polymerization and then were hydrolyzed to obtain oil-in-water Pickering stablizer. Based on phase separation mechanism, microcapsulated phase change material(MePCM) with PSt and PGMA composite shell were prepared by Pickering emulsion polymerization. The MePCM was characterized by large diameter(76 μm averagely), high core content[w(dodecanol)=83%] and excellent energy storage capability(phase change enthalpy of 174 J/g).

    Reprocessable and Self-healing Polybutadiene Rubber Based on Metal Coordination
    GUO Wenjin, WANG Xiaohan, LI Xiang, LI Yang, SUN Junqi
    2020, 41(9):  2090-2098.  doi:10.7503/cjcu20200215
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    To meet the requirements of high mechanical performance in various practical applications, rubber must be chemically cross-linked to form a 3D covalent network. However, the formation of a chemical cross-linked network classifies rubber as a thermoset material, which hinders the reshaping and recycling of rubber, causing waste of resource and severe environmental pollution. To solve this problem, a cross-linked network evolved from metal coordination interaction is introduced to the polybutadiene system to prepare a self-healing rubber material with admirable reprocessing ability. The self-healing rubber materials are fabricated by attaching carboxyl group to polybutadiene, followed by cross-linking through the metal coordination interaction between Zn2+ and carboxyl group (the resulting materials are denoted as PB-COOH/Zn2+). The PB-COOH/Zn2+ exhibits tensile stress of 6.30 MPa, ultimate strain of 2284%, Young’s modulus of 1.68 MPa, and toughness of 68.66 MJ/m3. Benefitting from high mobility of the polymer chain and excellent dynamic performance of the metal coordination interaction, PB-COOH/Zn2+ has excellent self-healing and recycling abilities. The mechanical properties of the damaged PB-COOH/Zn2+ almost completely recover after healing at 70 ℃ for 3 h. The healing efficiency of PB-COOH/Zn2+, which is defined as the ratio of the restored toughness to the original one, is 100%. In addition, PB-COOH/Zn2+ can be reprocessed by hot pressing at 70 ℃ with the pressure of 5 MPa for 10 min. The recycled PB-COOH/Zn2+ still maintains quite stable mechanical properties after three reprocessing processes. The mechanical properties of the metal coordination elastomer can be further improved by doping PB-COOH/Zn2+ with multi wall carbon nanotubs(MWCNTs). The Young’s modulus of the PB-COOH/Zn2+ doped with 40%(mass fraction) MWCNTs (denoted as PB-COOH/Zn2+/MWCNTs-40) is improved to 8.21 MPa. Doping with MWCNTs doesn’t affect the self-healing and recycling abilities of materials. The conductivity of MWCNTs endows the PB-COOH/Zn2+/MWCNTs with potential to transduce electrical energy into Joule heating energy to accomplish electro-thermal healing process and sensing application, which extend its potential applications as environmental-friendly materials.

    Preparation and Characterization of Graphene Oxide-sodium Alginate-chitosan Composite Scaffold
    WANG Bowei, MA Rui, WU Fan, LIU Zhihui, LI Lingfeng, ZHANG Xiao, LIU Dingkun, YANG Nan, LI Meihui, YANG Defeng, SUN Qi
    2020, 41(9):  2099-2106.  doi:10.7503/cjcu20200217
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    The composite scaffold material was constructed by freeze-drying technology from graphene oxide, sodium alginate and chitosan. The effects of graphene oxide content on the microstructure, porosity, swelling ratio, in vitro degradation performance, mechanical properties and biocompatibility of the scaffold materials were studied to determine the optimal graphene oxide content in the composite scaffold. The results show that the composite material has a solid sponge-like structure with a certain morphological plasticity. Scanning electron microscopy(SEM) observations show that each group of supports has a three-dimensional network structure. As the content of graphene oxide increased, the pore size gradually decreased and the pore wall thickness increased, the swelling ratio and degradation rate of the composite scaffold gradually decreased while the mechanical strength was significantly enhanced. Results of in vitro cytotoxicity showed that when the graphene oxide content was 0.3%(mass fraction), the cell survival rate was the highest, and when the graphene oxide content increased, the cell activity was significantly inhibited, causing cell death. Finally, the optimal content of graphene oxide in the composite scaffold is 0.3%. Our research lays a good foundation for the application of graphene oxide in bone tissue engineering materials.