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Table of Content

    10 June 2020, Volume 41 Issue 6
    Contents
    Cover and Content of Chemical Journal of Chinese Universities Vol.41 No.6(2020)
    2020, 41(6):  0-0. 
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    Review
    Single-molecule Imaging and Analysis of Signal Transduction Proteins on Cell Membranes
    LIANG Yuxin, ZHAO Rong, LIANG Xinyue, FANG Xiaohong
    2020, 41(6):  1127-1138.  doi:10.7503/cjcu20190663
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    Membrane proteins play an important role in cell signal transduction. Structural and functional abnormalities of membrane proteins can cause a variety of diseases. The development of single-molecule fluorescence imaging technology has enabled researchers to study the location and dynamic behavior of single membrane proteins in living cell systems, and their interactions with other molecules. Single-molecule fluorescence imaging technology has been widely used to reveal the molecular mechanisms of signal transduction under physiological conditions in recent years. Based on the our research work, this paper introduces the imaging principle, fluorescent labeling method and data analysis method of single-molecule fluorescence imaging in the study of cell membrane proteins, and further reviews the research progress of single-molecule fluorescence imaging on mechanistic study of several important signal transduction membrane proteins and related drug development.

    Water-soluble Regular Three-dimensional Supramolecular and Covalent Organic Polymers
    ZHANG Danwei, WANG Hui, LI Zhanting
    2020, 41(6):  1139-1150.  doi:10.7503/cjcu20190659
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    Recent research advances in the self-assembly of water-soluble three-dimensional supramolecular polymers, supramolecular organic frameworks, metal-supramolecular organic framework hybrids, metal-covalent-supramolecular organic framework hybrids and covalent organic framework and their functions as catalytic and delivering materials are described in this reveiw. The different kinds of supramolecular frameworks have been assembled through the hydrophobically driven encapsulation of cucurbit[8]uril macrocycles for the intermolecular dimers formed by the peripheral aromatic units of preorganized tetratopic or hexatopic components. The water-soluble covalent organic framework was prepared from a supramolecular organic framework template through the quantitative [2+2] cycloaddition of the alkene units incorporated in a tetrahedral component. In the final section, challenges and prospects for the future research in regular three-dimensional polymers are proposed.

    Construction of Controllable Lipid-DNA Complex for Study in Membrane Biology
    ZHANG Luhao, CAO Shuting, LIU Jiangbo, ZUO Xiaolei, WANG Lihua, FAN Chunhai, LI Jiang
    2020, 41(6):  1151-1162.  doi:10.7503/cjcu20200067
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    This review briefly summarized recent progress of lipid-DNA complexes, including their design, construction, and unique features. We highlighted their applications on living cell membranes, including dynamic membrane analysis, nanopores, live cell organization and interaction regulation, and drug delivery. We also summarized challenges in this field. We suggest that by using these lipid-DNA conjugates, cell membrane functions at the molecular level can be better understood and manipulated, which may facilitate the development of cell imaging, theranostics, construction of nanodevices and protocells.

    Application of Elastin-like Polypeptides in Supramolecular Assembly
    HOU Chunxi, LI Yijia, WANG Tingting, LIU Shengda, YAN Tengfei, LIU Junqiu
    2020, 41(6):  1163-1173.  doi:10.7503/cjcu20190667
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    Recent research progress of elastin-like polypeptides(ELPs) in temperature-responsive supramolecular structures is summarized systematically. The unique advantages of temperature controlled phase transition of elastin in the construction of supramolecular assembly are discussed and the sequence sensitivity of ELPs nanostructures is also demonstrated. Finally, the application of ELPs in supramolecular assembly in the future is prospected.

    Ruthenium Complexes with Photoresponsive Coordination Bonds for Light-controlled Surface Functions
    HUANG Yunshuai, YANG Ni, WU Zehong, WU Si
    2020, 41(6):  1174-1178.  doi:10.7503/cjcu20190655
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    We introduce ruthenium complexes with photoresponsive coordination bonds for light-controlled surface functions, including light-controlled surface patterns, manipulating protein adsorption and controlling wettability. Meanwhile, the fascinating features of photoresponsive Ru-ligand dynamic coordination bonds in surface functions are presented and their future applications are prospected.

    Recent Advances on High Mobility Emissive Anthracene-derived Organic Semiconductors
    XIE Ziyi, LIU Dan, ZHANG Yihan, LIU Qingqing, DONG Huanli, HU Wenping
    2020, 41(6):  1179-1193.  doi:10.7503/cjcu20190650
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    High mobility emissive organic semiconductors are the important core materials for the realization of organic light-emitting transistors(OLETs). However, it remains a long-standing challenge for developing high mobility emissive organic semiconductors because of the different molecular design requirements as well as their molecular packing in solid state. Recently, significant advance has been achieved in the development of high mobility emissive organic semiconductors, especially for the anthracene-derived high mobility emissive materials, which would lead to the rapid development of this field. In this article, we first give a brief introduction for the significant progress in the whole field, and then focus on special development of high mobility emissive anthracene-derivatives(more than 20 types) along with their molecular structure design, molecular packing and optoelectronic properties as well as their applications in OLETs. Finally, the challenges, development directions and opportunities are discussed. Hopefully, this review would give a valuable guideline for the further research in this field.

    Preparation and Applications of Stretchable and Tough Hydrogels
    SHENG Hui, XUE Bin, QIN Meng, WANG Wei, CAO Yi
    2020, 41(6):  1194-1207.  doi:10.7503/cjcu20190656
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    In this review, we focus on the design principle of stretchable and tough hydrogels as well as the applications in the fields of tissue engineering and flexible electronic devices. Through connecting hydrogel network structures, toughening mechanisms and chemical structures with macroscopic mechanical properties, we mainly discussed the research progress of single network hydrogel, double network hydrogel, nanocomposite hydrogel and so on. The summary and outlook of the new ideas and directions of stretchable and tough hydrogels were also demonstrated at last.

    Article
    Preparation of High-surface-area Hierarchically Porous γ-Al2O3 by One-step Hydrolysis of Metal Alkoxide and Performance
    LIU Siming, WANG Jiannan, YU Shen, LIU Zhan, WANG Zhao, LI Xiaoyun, CHEN Lihua, SU Baolian
    2020, 41(6):  1208-1217.  doi:10.7503/cjcu20200076
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    Ultrahigh-surface-area γ-Al2O3 materials with special morphologies and hierarchically porous structures were prepared at room temperature by one-step hydrolysis of metal alkoxide under different aqueous organic solvents systems. With the aid of X-ray diffraction(XRD), N2 adsorption-desorption, scanning electronic microscopy(SEM) and transmission electron microscope(TEM), it was proved that the hydrolysis and condensation process of aluminum tri-sec-butoxide and the diffusion behavior of by-product alcohol molecules could be precisely controlled by the water content and the type of solvent, thereby the product structure were optimized in return. The results show that the γ-Al2O3 material with straight macroporous wall and 3D-mesporous was obtained under the water/acetonitrile system, meanwhile, the smooth, flaky and wrinkled morphologies appeared in the macroporous wall in turn as the water content increased. However, only 3D-mesporous structure stacked with 10 nm-thick flaky γ-Al2O3 could be observed for the material prepared under the saturated butanol solution system with the specific surface area of up to 517 m 2/g. Besides, the macro-mesoporous γ-Al2O3 material prepared under the 3 mL water content in the water/acetonitrile system was selected as the carrier for Pt-based catalyst. The carrier structure basically remained intact after the loading process and metal Pt nanoparticles were uniformly dispersed on the carrier. The hierarchical γ-Al2O3 supported Pt-based catalyst showed better hydrodemetallization performance than the commercial boehmite supported catalyst, and the Ni and V removal rate increased by 11.62% and 10.83%, respectively.

    Article: Inorganic Chemistry
    Preparation of CuS/Ag2S Nanocomposite and the Peroxidase-like Properties
    WANG Ruixue, YIN Dongmei, SONG Yongxin, SHAN Guiye
    2020, 41(6):  1218-1223.  doi:10.7503/cjcu20200035
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    Amicrosphere-shaped CuS/Ag2S nanocomposites were synthesized by hydrothermal method. The morphology and optical properties of CuS/Ag2S nanocomposites were characterized by transmission electron microscopy, UV-Vis absorption spectroscopy, and Raman spectroscopy. The peroxidase-like properties were investigated, and peroxidase-like reactions catalyzed by CuS/Ag2S nanocomposite were detected by surface-enhanced Raman scattering in situ. The colorimetric reaction was performed using 3,3',5,5'-tetramethyl-benzidine(TMB) as a substrate, and it was proved that CuS/Ag2S nanocomposite has peroxidation-like properties in the presence of hydrogen peroxide(H2O2) which can oxidize colorless TMB to blue oxTMB. And the detection of H2O2 are realized.

    Controllable Synthesis of SAPO-5 Molecular Sieves and Exploration of the Crystallization Process
    HE Zhechao, XIA Kun, WANG Jing, ZHOU Dan, LU Xinhuan, XIA Qinghua
    2020, 41(6):  1224-1230.  doi:10.7503/cjcu20200022
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    SAPO-5 molecular sieves were synthesized in non-acetic acid systems through rotating and static crystallization routes, respectively. The effects of rotation speed, crystallization time and water-silicon ratio of the gel system on the crystallization process of SAPO-5 samples were explored. The crystallization process of SAPO-5 samples under static and rotating hydrothermal conditions were studied by XRD and SEM. The results show that SAPO-5 samples obtained under the static hydrothermal conditions for 6 h is spherical and hexagonal columnar aggregated crystals. While the SAPO-5 samples obtained at 20 r/min for 2 or 6 h are dispersed concave columnar crystals(about 6—8 μm in diameter) and uniformly dispersed spherical crystals(16 μm in diameter), respectively. And SAPO-5 samples obtained at 60 r/min by extending the crystallization time to 3 h is hexagonal columnar crystal(about 5—8 μm in diameter). Also, hexagonal columnar SAPO-5 samples can be obtained by crystallizing at a rotation speed of 100 and 140 r/min for only 1 h. In addition, this work by adjusting the water-silicon ratio, the optimal water-silicon ratio was determined to be 70(the crystal phase is pure and the molecular sieve has the best dispersion from the morphology). In summary, compared to static crystallization, rotational crystallization not only improves the dispersion of the crystal from the morphology, but also improves the crystallization efficiency of SAPO-5 samples through shortening the crystallization time and reducing the crystallization speed. At the same time, SAPO-5 samples was synthesized in a non-acetic acid system with a smaller water-silicon molar ratio(70) and a lower amount of template agent, which provided a simpler and economical method for the synthesis of SAPO-5 molecular sieve.

    Differences of Growth and Cytotoxicity of Calcium Oxalate Crystals Formed on HK-2 Cells Under Different Oxalic Acid/Calcium Ratios
    LIU Hong,ZOU Guojun,SUN Xinyuan,OUYANG Jianming
    2020, 41(6):  1231-1242.  doi:10.7503/cjcu20190713
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    We investigated the growth differences of CaOx crystals with different oxalic acid/calcium(Ox/Ca) molar ratios on the surface of human renal proximal tubule epithelial cells(HK-2) before and after injury and the toxicity of the crystals formed on the cells. CaOx supersaturated solution caused further damage to both the normal and damaged cells, resulting in the decrease of cell viability, lysosomal integrity and mitochondrial membrane potential, while the increase of intracellular reactive oxygen species(ROS), cytoskeleton disorder, phosphatidylserine(PS) eversion ratio and osteopontin(OPN) expression. With the increase of Ox/Ca molar ratio in saturated solution, the cell damage increased. Normal cells mainly induce the formation of calcium oxalate dihydrate(COD) crystals, and the percentage of COD is positively correlated with the Ox/Ca ratio. Damaged cells mainly induced calcium oxalate monohydrate(COM), and the number and aggregation of crystals are positively correlated with Ox/Ca molar ratio. Compared with the control group cells, the crystal edges induced by the damaged group cells are sharper, and the damage of sharp crystals to the cells is greater than that of round and blunt crystals. The results of this study suggest that reducing the supersaturation of CaOx, reducing the Ox/Ca molar ratio and repairing the damaged renal epithelial cells are all beneficial to inhibit CaOx stone formation.

    Analytical Chemistry
    On-chip Sorting of Beads with Different Magnetic Responsiveness by Lateral Magnetophoresis
    ZHANG Zuoran, ZHANG Li, ZHANG Zhiling
    2020, 41(6):  1243-1251.  doi:10.7503/cjcu20200080
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    Magnetic separation is widely used in biochemical analysis. The separations of multiple small targets by magnetic force still remain a challenge. To solve the problem, different types of magnetic probes coupled with small targets have to be sorted. Here, we propose a strategy to separate magnetic nano-beads(MNs) with either a strong or weak magnetic responsiveness on a chip system. The sorting principle is utilizing the lateral magnetophoresis of MNs. A theoretical model is proposed to analyze the lateral displacement of MNs including aggregation and deflection. On this basis, chips were designed to separate MNs. By adjusting the flow rates, MNs with different magnetic responsiveness were sequentially separated. The sorting efficiency is acceptable and the procedure is easy to perform. MNs with strong magnetic responsiveness can be completely separated, which is valuable for rare targets sorting. The system was applied to sort DNA from hepatitis B virus(HBV) and complementary DNA from hepatitis C virus(HCV) simultaneously. This system has the potential for wide application in biochemical analysis.

    Quantitative Analysis of MicroRNA Content by Fluorescence Imaging in Cancer Cells Using Dual-color Fluorescence Nanosensor
    BAI Cuiting, YUE Renye, LUO Liegao, MA Nan
    2020, 41(6):  1252-1261.  doi:10.7503/cjcu20200026
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    MicroRNA(miRNA) plays an important role in cellular function and gene expression with abnormal expression level or varieties. Given this, miRNA imaging in cancer cells was regarded as the effective approach for disease diagnosis and treatment. Herein, we built a sensitive nanosensor with gold nanoparticles(GNP) and two type of dye-modified DNA, FAM-DNA2 and Cy5.5-DNA3. DNA4 containing photocleavable linker(PC-linker), was used as the bridge for self-assembly of nanosensor. 302 nm UV light was used as the startup switch. Cy5.5-DNA3 was released from assembly with the irradiation of UV light, the fluorescence intensity was used as internal reference signal to standardize the quantity of nanoparticles into cells. MiRNA-21 that working as catalytic molecule can induce the assembly of nanosensors, resulting to release FAM-DNA2 in the presence of Fuel DNA, at the same time, the recovery fluorescence of FAM was used as detection signal. By combination of the fluorescence intensity of FAM and Cy5.5(FLFAM/FLCy5.5), we can calculate the quantity of miRNA and nanosensors in cancer cells, which avoided the existence of background signal caused by the different contents of intracellular nanoparticles. Importantly, this nanosensor is of great stability, biocompatibility, and can be used for cellular fluorescence imaging. In addition, the limit of detection(LOD) was about three orders of magnitude lower than traditional non-catalytic method and calculated to be 23.1 pmol/L. The quantity of miRNA-21 in Hela cells was calculated to be 0.0236 nmol/L.

    Physical Chemistry
    Selective Oxidation of Atomically Dispersed Fe-N-C Catalyst Under Mild Conditions
    XIONG Junyu, WANG Shanshan, XU Yanqing, HU Changwen
    2020, 41(6):  1262-1268.  doi:10.7503/cjcu20200149
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    An atomically dispersed Fe-N-C catalyst prepared by one-pot mechanochemical process was used for selective oxidation of sulfides and secondary alcohols. The results show Fe-N-C catalyst can selectively transform sulfides to sulfoxides under mild conditions without any over-oxidized sulfones. This process has several advantages such as mild reaction conditions, high reaction speed and satisfactory yields. In addition, this catalyst exhibits high catalytic activity in the oxidation of the secondary alcohols to the related ketones with decent yields. As a heterogeneous catalyst, activity of this atomically dispersed Fe-N-C does not significantly decrease after 5 times of circulation.

    Preparation and Enhanced Dielectric-hydrophobic Properties of PDMS-PVDF Composite Films with Au@PS Nanoparticle
    ZHANG Qilong, YAO Liqin, ZHU Zhicai, ZHANG Zhao, YANG Hui
    2020, 41(6):  1269-1276.  doi:10.7503/cjcu20200102
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    Au nanoparticles were uniformly loaded on the surface of polystyrene(PS) microspheres with an average diameter about 250 nm via the emulsion polymerization and reduction method. The PS/Au was homogeneously mixed with polydimethylsiloxane(PDMS)/poly(vinylidene fluoride-co-trifluoroethylene)[P(VDF-TrFE)](mass ratio: 2∶3) by solution blending method, and the dense composite film with uniform distribution of Au@PS particle and micro bulge surface were obtained. The effects of Au@PS doping content on composite films structure, melting crystallization behavior and dielectric-hydrophobic properties were investigated. It was found that the introduction of Au@PS nanoparticles hinders the β phase formation of P(VDF-TrFE), but has no obvious effect on the bonding structures. The crystallization temperature and glass-transition temperature of composite films increases, and their melting point decreases slightly with increasing the Au@PS content. Due to the synergistic effect of interface polarization and micro capacitance, the dielectric constant of composite film with Au@PS nanoparticles is significantly increased. The Au nanoparticles uniformly loaded on the surface of PS sphere reduce the formation of conductive network, thus maintain a relatively low dielectric loss value. Typically, the dielectric constant of the blend film with 5%(mass fraction) Au@PS nanoparticle reaches 22 at 100 Hz, which is 8.8 and 3.14 times that of pure PDMS and PDMS/P(VDF-TrFE), respectively. The blend film with 5%Au@PS also possesses a large contact angle of 112.31° due to the interaction of hydrophilic Au nanoparticles and the existence of micro bulge structure. All the improved performances show great potential application for electrowetting devices.

    Influences of Electron Donating Groups on the Photophysical Properties of NNI-R Series Molecules
    LIN Guifeng,GUO Jingfu,HE Tengfei,REN Aimin
    2020, 41(6):  1277-1286.  doi:10.7503/cjcu20200086
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    A series of N-phenyl-1,8-naphthalimide derivatives with different electron donating groups(NNI-R) were designed and studied. The geometric and electronic structures as well as room phosphorescent performance were comparatively studied in dichloromethane solvent and the gas phase. It should be emphasized that in polar solvent(dichloromethane solvent), the NNI-Rs have two isomers of the S1 state, one has charge-transfer(CT) character, the other has localized excitation(LE) feature. For NNI-R with R=OMe or OH, the total energy of the structure with LE character is far lower than the one of CT structure. which will inhibit intersystem crossing(ISC), and the room temperature phosphorescence will not happen. In the gas phase, all the first singlet excited states of NNI-R have only stable geometry with CT characters, which significantly inhibit the fluorescence(FL) rate and effectively promote the ISC rate. Phosphorescence emission becomes a possibility for NNI-R series molecules at room temperature. As a result, this work likes to contribute to a reliable theoretical basis for the synthesis and characterization of pure organic room temperature phosphorescent materials based on N-phenyl-1,8-naphthalimide.

    Material Chemistry
    Enhancing Hydrogen Evolution Performance of a Regular Cube NiCu Nanocrystalline Electrocatalyst Fabricated by Normal Pluse Electrodeposition
    SUN Qiangqiang, CAO Baoyue, ZHOU Chunsheng, ZHANG Guochun, WANG Zenglin
    2020, 41(6):  1287-1296.  doi:10.7503/cjcu20200082
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    Herein, a regular cube structured nickel-copper alloy electrocatalyst on nickel foam(NF) with phase-separated metallic Ni and Cu as the main crystal phase, and the average particle size of 70 nm, denoted as NiCu/NF, was prepared by normal pluse voltammetry. The as-obtained catalyst displays superior electroca-talytic activity towards hydrogen evolution reaction(HER), requiring an overpotential of merely 86 mV to afford 10 mA/cm 2 current density in 1 mol/L KOH. Moreover, NiCu/NF exhibits remarkable stability with a potential fluctuation of merely 12 mV during a 24 h continuous HER electrolysis. As a result, the two-stage composite cube-nanocrystalline structure gives rise to the 14.5-fold increased electrochemical active surface area(ECSA), exposing a huge number of catalytic active sites for HER, providing sufficient channels for charge transfer and material transfer on the electrode surface. On the other hand, the strong synergistic effect induced by Cu-introduction and the formation of NiO/Ni heterojunction brings prominent improvement of intrinsic HER activity of electrode materials via alteration of the electronic property of the adjacent Ni atoms. The three factors contribute collectively to the superior electrocatalytic performances of NiCu/NF electrode towards HER. Meanwhile, NiCu/NF electrode follows the Volmer-Heyrovsky mechanism with the reaction rate determined by the electrochemical desorption of hydrogen adsorbent on the electrode surface during HER. This study provides a new perspective for multi-structural nanoscale synthesis and promotes the development of NiCu-based electrode materials in energy conversion applications.

    Physical Chemistry
    Effect of Surface Cu0 Content of the Catalysts on CO2 Hydrogenation to C2+ Alcohols
    ZHANG Weizhong,WEN Yueli,SONG Rongpeng,WANG Bin,ZHANG Qian,HUANG Wei
    2020, 41(6):  1297-1305.  doi:10.7503/cjcu20200061
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    Pyrolyzing metal organic framework(MOF) material Fe-MIL-88B loaded with Cu in air atmosphere, uniformly dispersed CuFe based catalysts with different Cu and Fe valence distribution were gained at different reduction temperatures. The structure of the catalysts were characterized by means of X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), H2 temperature program reduction(H2-TPR), N2 adsorption-desorption(BET), scanning electron microscopy(SEM), and high resolution transmission electron microscopy(HRTEM). The catalytic performances of CO2 hydrogenation to C2+ alcohols were investigated on a fixed-bed reactor. It was found that the higher the reduction temperature was, the more percentage of Cu and Fe with lower valence state was on the surface of the catalysts. When the reduction temperature was 350 ℃, Cu0/(Cu++Cu0) was 73.9 %, and 0.4% Fe 0 appeared, the catalytic performance was the best, where the CO2 conversion rate was 6.82%, the total alcohol selectivity was 39.4%, and the molar percentage of C2+ alcohol was 95.1%.

    Preparation and Electrochemical Properties of S@C Composite Material with High Capacity and Ordered Alignment of Channels
    BAI Yanqun,WANG Cunguo,LI Xue,FAN Wenqi,SONG Penghao,GU Yuanchun,LIU Faqian,LIU Guangye
    2020, 41(6):  1306-1312.  doi:10.7503/cjcu20200055
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    The wood was pretreated with ammonia to remove the lignin from the wood, then heated under the protection of inert gas and activated by KOH, the three-dimensional(3D) carbon material with ordered alignment of channels and multi-pores was obtained. After melting and absorbing sulfur in a autoclave at 150 ℃, a kind of S@C composite electrode material with high capacity was prepared. The composite was characterized by scanning electron microscopy(SEM), X-ray diffraction(XRD), Raman spectroscopy and N2 adsorption-desorption analysis. The results show that the carbon material has a 3D structure with anisotropic channels and multi-level pores. The channels are arranged orderly in parallel with the growth direction of the tree trunk. In addition, there are many micropores on the inner wall of the carbon material activated by KOH. So the material has high pore volume and specific surface area. Furthermore, the Li/S battery was assembled by using S@C composite as cathode material. The electrochemical results show that the first discharge capacity of the S@C composite electrode material reaches 1595 mA·h /g, which is close to the theoretical specific capacity of sulfur electrode material(1670 mA·h/g).

    Fractal Characteristics of the Microstructures of Three Hydrophobic Surfaces with Steel Substrate and Their Effects on Wettability
    JIANG Huayi,LIU Mei,QI Hongyuan,LIANG Aiguo,WANG Yulong,SUN Nana,WU Zhe
    2020, 41(6):  1313-1319.  doi:10.7503/cjcu20200050
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    The microstructures on 304 stainless steel, X80 pipeline steel and 45# steel surfaces were prepared at different etching times by using the chemical etching and modification with low-surface-energy material. The microstructures and wettabilities of different material surfaces were obtained by a scanning electronic microscope and a contact angle meter, respectively. The fractal parameters were calculated by Matlab software. The results showed that the hydrophobic surfaces prepared on three materials had fractal characteristics. The optimal etching time was 30 min. At that time, the maximum subset of multifractal spectrum was close to the leftmost, the corresponding singularity index was the smallest, and the fractal dimension also reached the maximum. The linear fitting results of fractal dimension and contact angle was good. The contact angle increased with the increase of fractal dimension.

    Effects of Hydrothermal Reaction Conditions on the Structure and Properties of Porous Spherical Bi2WO6 Photocatalyst
    WANG Rui,XU Mei,XIE Jiawen,YE Shengying,SONG Xianliang
    2020, 41(6):  1320-1328.  doi:10.7503/cjcu20200007
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    Bi2WO6 photocatalysts were prepared via hydrothermal method. The effects of hydrothermal reaction temperature, hydrothermal time and pH value of precursor solution on the catalytic activity of the catalysts for ethylene degradation under visible-light irradiation were investigated. The crystal composition, micro-morphology and optical properties were characterized by X-ray powder diffraction(XRD), scanning electron microscopy(SEM), UV-Visible diffuse reflectance spectroscopy(UV-Vis DRS) and BET surface area analysis. The results show that at the conditions of 120 ℃, 12 h, pH=0.5, the Bi2WO6 photocatalyst undergoes anisotropic growth and Ostwald ripening process to form a porous microsphere structure self-assembled by two-dimensional nanosheets, which effectively increases the contact area with ethylene gas. The band gap width of the catalyst is reduced to 2.86 eV, and the visible light response range is widened. The degradation rate of ethylene reached 13.69% with in 240 min under visible light irradiation.

    Nano-Al2O3 Coated Li-rich Cathode Material Li1. 2Ni0.13Co0.13Mn0.54O2 for Highly Improved Lithium-ion Batteries
    CHEN Liangdan,ZOU Wei,WU Liang,XIA Fanjie,HU Zhiyi,LI Yu,SU Baolian
    2020, 41(6):  1329-1336.  doi:10.7503/cjcu20190719
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    The lithium-rich cathode material Li1.2Ni0.13Co0.13Mn0.54O2 were coated uniformly by nano-Al2O3 for highly stable lithium-ion batteries. The optimum content of nano-Al2O3 coating on the structure, surface morphology and electrochemical properties were systematically studied by X-ray diffraction(XRD), scanning electron microscopy(SEM) and transmission electron microscopy(TEM). SEM and TEM results show that the surface of the lithium-rich cathode material is evenly coated with nano-Al2O3. XRD results show that the as-synthesized materials have a layered structure. Electrochemical test results show that the nano-Al2O3 coating is beneficial to improving the discharge specific capacity, rate performance and cycle stability. The nano-Al2O3 coated Li1.2Ni0.13Co0.13Mn0.54O2 material has a specific discharge capacity of 249. 7 mA·h/g with excellent cycling stability(89.5% capacity retention after 100 cycles). Cyclic voltammetry(CV) and electrochemical impedance(EIS) results show that nano-Al2O3 coating can effectively inhibit the erosion of HF, reduce electrode material/electrolyte interface side-reactions, decrease polarization, reduce interface impedance and charge transfer impedance. This work suggests that the nano-Al2O3 coating is an effective route to significantly improve the electrochemical performance of lithium-rich cathode materials.

    Preparation and Characterization of Tannin/Zwitterionic Modified Oil-water Separation Membrane
    PENG Xinyan, LIU Yunhong, LI Jiawen, FENG Yilong, WANG Hanchun
    2020, 41(6):  1337-1344.  doi:10.7503/cjcu20190706
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    Based on the chemical properties of tannic acid and the special wettability of zwitterionic groups, we successfully prepared the ultrahydrophilic and underwater ultraoleophobic separation membrane. The stainless steel mesh was used as substrate, which was grafted by zwitterionic polymers after pre-treatment with tannic acid. The micro-chemical structure and wettability of the oil-water separation membrane were characterized by X-ray photoelectron spectroscopy(XPS), scanning electron microscope(SEM), and contact angle mea-suring instrument. The results show that zwitterionic groups were grafted through chemical bonding. The obtained oil-water separation membrane enable an efficient and energy-saving separation for various oil-water mixture by gravity-driven. Meanwhile, the membrane demonstrates excellent chemical stability and recyclability.

    Influential Factors of La-doped Calcium Titanate for Photocatalytic H2 Evolution Under Visible Light
    CHENG Rongmin,XU Hong,SHAN Ruiping,ZHAN Conghong
    2020, 41(6):  1345-1351.  doi:10.7503/cjcu20190644
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    For photocatalytic H 2 evolution from water splitting, perovskite photocatalyst Ca 0.99La 0.01TiO 3 was prepared by sol-gel method with citric acid as complexing agent. The influence of N doping on photocatalytic activity was investigated. The hydrogen-producing capacity of Ca 0.99La 0.01TiO 3- xN x with different Pt loading and different kinds of sacrificial agents was also investigated under visible light irradiation. The photocatalytic materials were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM), UV-Vis diffuse reflectance spectroscopy(UV-Vis DRS). The results show that under the irradiation of visible light, the perovskite photocatalyst Pt-Ca 0.99La 0.01TiO 3- xN x with 1% Pt-loading has the highest photocatalytic activity of hydrogen production from water when Na 2SO 3/Na 2S is used as the sacrificial agent. Pt-loading promotes photocatalytic reaction and improves photocatalytic activity.

    Effect of Organic Carbon Source on Performance of LiTi2(PO4)3/C Composite Electrodes in Aqueous Solutions
    ZHANG Chenyang,WEN Yuehua,ZHAO Pengcheng,CHENG Jie,QIU Jingyi,SUN Yanzhi
    2020, 41(6):  1352-1361.  doi:10.7503/cjcu20190624
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    Spherical LiTi2(PO4)3/C composites were prepared through spray drying method followed by high-temperature calcination and used as anodes for aqueous lithium ion batteries. The effect of different organic carbon source based on different coating mechanisms and carbon content on the electrochemical properties of LiTi2(PO4)3/C composite anodes were investigated. Results show that if the amount of carbon coating is too low, it cannot prevent water from eroding. In contrast, if the amount of carbon coating is too high, the resis-tance of lithium ion diffusion will be high. So the optimal carbon coating amount of LiTi2(PO4)3/C electrodes is 13%. The uniformity of carbon coating and the thickness of coating layer are the two main factors affecting the performance of coated electrodes. The polydopamine-coated lithium titanium phosphate particles based on the in-situ polymerization coating mechanism are the most uniform, and the microcrystalline structure and electronic conductivity after carbonization is better. The best performance is achieved by LiTi2(PO4)3/C anodes prepared by using polydopamine as the carbon source.

    Preparation and Electrocatalytic Performance of Carbon Material Co-doped by Bimetal Phosphide and Heteroatom
    JIN E,SONG Kaixu,CUI Lili
    2020, 41(6):  1362-1369.  doi:10.7503/cjcu20190562
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    A kind of aniline pentamer with high nitrogen content was used as ligand to prepare Fe/Co-MOF loading on nickel foam through solvothermal method. Fe2P, Co2P, N and P modified carbon material(Fe/Co/P-NPs) was obtained by phosphating reaction with Fe/Co-MOF as metal and carbon sources. Scanning electron microscopy(SEM), transmission electron microscopy(TEM), X-ray photoelectron spectroscopy(XPS) and X-ray diffraction analysis(XRD) were employed to characterize the morphology and structure of the materials. The electrocatalytic activity and stability of the materials were characterized by cyclic voltammetry(CV) and linear sweep voltammetry(LSV). It is found that Fe/Co/P-NPs display good catalytic activity in oxygen evolution reaction, with over potentials of 270 and 300 mV to deliver 10 mA/cm 2 and 100 mA/cm 2 current density, respectively, proving the better activity than that of RuO2. Importantly, it requires 1.48 V to reach the current density of 10 mA/cm 2 and shows good stability in alkaline solution.

    Polymer Chemistry
    Preparation and Performance of Self-standing NH2-MIL-125/polyoxadiazole Composite Forward Osmosis Membranes
    HE Nan, LIU Wei, YANG Xia, WANG Xianze, CUI Xiaochun, WU Jinghui, GENG Zhi
    2020, 41(6):  1370-1377.  doi:10.7503/cjcu20190697
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    A high-strength hydrophilic carboxyl-containing polyoxadiazole material(POD-COOH) and an amino-containing metal organic frame material(NH2-MIL-125) were synthesized first, then a series of novel self-standing composite forward osmosis membranes were prepared using NH2-MIL-125 as filler and POD-COOH as matrix by solution blending and casting method. Further the effects of NH2-MIL-125 introduction on the structure and performance of composite forward osmosis membranes were investigated. The results demonstrated that the prepared self-standing composite forward osmosis membranes had a dense homogeneous structure. The hydrophilicity and electronegativity of the membranes were improved with increasing NH2-MIL-125 content. And the composite membranes maintained good mechanical properties. When the testing feed and draw solutions were pure water and 1.5 mol/L Na2SO4 solution respectively, the prepared self-standing composite membranes exhibited excellent forward osmosis performance, which is attributed to the elimination of internal concentration polarization existing in support layer of traditional forward osmosis membranes.

    Investigation of Formation Mechanism of Polydopamine by Adding Free Radical Quencher
    WANG Qianying, CUI Shuxun
    2020, 41(6):  1378-1383.  doi:10.7503/cjcu20190696
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    In this paper, by using dimethyl sulfoxide(DMSO) and edaravone as the free radical quencher, the free radical polymerization pathways of dopamine under different pH conditions were studied. Besides, the absorbance of the dopamine solutions was characterized by means of UV-Vis spectroscopy. It is found that the dopamine polymerization rate decreases with the increase of the DMSO concentration, indicating that DMSO can slow down the polymerization of dopamine. Further experiments show that edaravone can slow down the polymerization of dopamine more significantly. These results indicate that the free radical polymerization is one of the possible pathways of dopamine polymerization. Although DMSO can slow down the polymerization of dopamine, it cannot completely restrain the polymerization, which indicates that the polymerization has other reaction pathways besides the free radical polymerization. These pathways may be the main reason for the structure complexity of polydopamine. Moreover, it is found that the polymerization rate increases with the increase of pH and the final reaction products under different pH conditions are similar.

    Material Chemistry
    A Photoresponsive Azobenzene-functionalized Covalent Organic Framework
    LI Shanshan, ZHAO Wenjuan, LI Hui, FANG Qianrong
    2020, 41(6):  1384-1390.  doi:10.7503/cjcu20200021
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    Covalent organic frameworks(COFs) with high specific surface area, regular structure, and modi-fiable pore channels, are crystalline porous organic polymers and have been widely used in various fields. Azobenzene derivatives with light isomerization characteristics are important stimulus-responsive materials. Herein we report a method of postsynthetic modification for the preparation of photothermal responsive azobenzene-functionalized COF, denoted as JUC-501(JUC=Jilin University China), which based on introducing small azobenzene molecules into the channels of COF(JUC-500). Under ultraviolet irradiation and heating conditions, the COF with azobenzene in the pores will undergo reversible cis-trans isomerization reaction and exhibits excellent reversible capture and release properties for methyl orange(MO).

    Novel Biosynthesis Method of Silver Nanoparticle by UV Radiation of Cornus Officinalis Aqueous Extract and Biological Activities
    WEI Simin,WANG Yinghui,TANG Zhishu,SU Rui,HU Jinhang,GUO Hui,LI Chen,JIANG Jintao,SONG Zhongxing
    2020, 41(6):  1391-1398.  doi:10.7503/cjcu20190721
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    Owing to the widely applications of silver nanoparticles(AgNPs) in catalysis and biomedicine, researchers have focused their attentions on the formation method. In this work, a green and easy synthesis method of silver nanoparticles(AgNPs) by 254 nm ultraviolet lamp radiation using Cornus officinalis aqueous extract was reported, and the antioxidant, antibacterial and anticancer activities were assessed. The influence of the solution pH(7.0), material proportion(1∶1) and reaction time(1 h) on reduction reaction were discussed to confirm the most efficient reaction condition. X-ray diffraction(XRD), dynamic light scattering and transmission electron microscopy were conducted to investigate the shape, size and surface of the silver nanoparticles, revealing a face-centered cubic(fcc) structure and spherical shape with an average particle size of (55.4±0.9) nm covered by anion(Zeta potential: -10.2 mV). By calculating the free radical scavenging rate for DPPH, the antioxidant activities of AgNPs were assessing. When the concentration of AgNPs increased to 62.5 μg/mL, the free radical scavenging rate was 70% meaning a good antioxidant activity. Furthermore, the AgNPs generated by Cornus officinalis aqueous extract revealed significant inhibition on the growth of S. aureus and E. coli, where the MIC values were 3.9 and 7.8 μg/mL, respectively. The IC50 values for colorectal cancer cell HCT116 and SW620 were 23.1 and 35.1 μg/mL, respectively, indicating a good anticancer activity.

    Synthesis and Electrochromic Performance of Phosphazene-viologen Polymer
    SUN Mengying,Lü Jingchun,XU Hong,ZHANG Linping,ZHONG Yi,CHEN Zhize,SUI Xiaofeng,MAO Zhiping
    2020, 41(6):  1399-1406.  doi:10.7503/cjcu20190541
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    Electrochromic materials have attracted considerable attention due to their versatile applications in academic and industrial areas. In this work, a novel organic-inorganic hybrid electrochromic material(denoted as PHV 2+) was synthesized, which contains six viologen moieties and a hexachlorocyclotriphosphazene core. The structure of the polymer was characterized by Fourier transform infrared spectroscopy(FTIR), X-ray diffraction(XRD) and nuclear magnetic resonance. The water solubility makes it possible to construct an electrochromic hydrogel with polyvinyl alcohol by a simple method, which has the advantages of low cost and no toxicity. The electrochromic device made of this polymer exhibits good electrochromic properties with good cyclic stability. The device undergoes a noticeably yellowish-purple color change at a voltage of 2.1 V. The optical contrast of the device is 62.19% at 526 nm. This electrochromic polymer shows its potential in electrochromic application.