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    10 August 2022, Volume 43 Issue 8
    Content
    Cover and Content of Chemical Journal of Chinese Universities Vol.43 No.8(2022)
    2022, 43(8):  1-8. 
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    Review
    Research Progress of Controllable Self-assembled DNA Origami Structure as Drug Carrier
    WU Yushuai, SHANG Yingxu, JIANG Qiao, DING Baoquan
    2022, 43(8):  20220179.  doi:10.7503/cjcu20220179
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    In the past few decades, structural DNA nanotechnology, as a rapidly developing, controllable self- assembling strategy, enables the design and construction of a variety of sophisticated nanostructures. Particularly, DNA origami structures feature unique properties, such as rationally designed geometry, precise spatial addressabi?lity, easy of modification and good biocompatibility, which provide them with broad prospects in drug delivery. In this minireview, the research progresses of drug delivery systems based on the DNA origami technique were summarized. The future development prospects of DNA origami nanocarriers and remaining challenges in this field were also discussed.

    Ordered Mesoporous Materials: History, Progress and Perspective
    GUO Cheng, ZHANG Wei, TANG Yun
    2022, 43(8):  20220167.  doi:10.7503/cjcu20220167
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    Ordered mesoporous materials with pore diameters ranged from 2 nm to 50 nm possess ordered mesostructures, high surface areas, large pore volumes and tunable compositions, which have received great research interests in many fields. In the past decades, the precise synthesis, rational design, and controllable functionalization of ordered mesoporous materials have made great progresses, thereby laying a solid foundation for the practical applications, including energy storage and conversion, catalysis, biomedicine, and sensing. This review first summarizes the development history of ordered mesoporous materials comprehensively, and the milestones in this field are reviewed in detail. After that, based on the structure-property relationship, the latest progresses of ordered mesoporous materials in emerging fields, such as energy, catalysis and biomedicine are overviewed. In the last, the research challenges in this field are presented and the future perspectives are outlined.

    Progress on the Stretchable Composite Solid Polymer Electrolytes
    LUO Xinyan, JIA Ruonan, XIANG Yong, ZHANG Xiaokun
    2022, 43(8):  20220149.  doi:10.7503/cjcu20220149
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    The wearable electronics require flexible batteries to serve as power sources with high energy density, capacity, safety, and reliability. Stretchable solid electrolytes with high ionic conductivity are key to developing flexible all-solid-state lithium batteries which meet the above requirements. This paper reviews the typical mechanisms and recent progress on enhancing the ionic conductivity of composite solid polymer electrolytes. The strategies for decoupling the ionic conductivity and stretchability of solid polymer electrolytes are also discussed. The advanced characterization tools which may help to promote the study on stretchable composite solid polymer electrolytes are briefly introduced. Finally, the future trends and important directions of the technologies of stretchable composite solid polymer electrolytes are proposed as well.

    Azobenzene-integrated DNA Nanomachine
    LIU Suyu, DING Fei, LI Qian, FAN Chunhai, FENG Jing
    2022, 43(8):  20220122.  doi:10.7503/cjcu20220122
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    Azobenzene-integrated DNA nanomachines have inherited the photo-isomerized and hypoxia-responsive properties of azobenzene, thus enriching methodological toolboxes for designing dynamically responsive nanodevices. However, fabrication of azobenzene-based DNA nanomachine remains challenging due to the limitation of the response mechanism of azobenzene derivatives. This review elaborated the construction methods and corresponding advantages and drawbacks of azobenzene-integrated DNA nanomachine, and summarized the design rules of azobenzene-based DNA nanomachine with visible light-responsive behaviors. Further, the applications of azobenzene-based DNA nanomachine in regulating the activity of biological enzyme, material transport, mechanical motion were reviewed. We expect that this review can facilitate the development of more flexible coupling methods between azobenzene and DNA, and bring inspiration for the biomedicine application of azobenzene-integrated DNA nanomachine.

    Article: Inorganic Chemistry
    Efficient Preparation of Mesoporous γ-Al2O3 Microspheres and Performance of Pd-loaded Catalysts
    TAN Yan, YU Shen, LYU Jiamin, LIU Zhan, SUN Minghui, CHEN Lihua, SU Baolian
    2022, 43(8):  20220133.  doi:10.7503/cjcu20220133
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    Porous γ-Al2O3 has been widely used as the support material due to its ultrahigh specific surface area, strong adsorption capacity and great thermal stability. However, owing to a series of problems existing in the synthesis process of porous γ-Al2O3 materials, like complex preparation method, high energy consumption, low purity and serious environmental pollution, it is important to develop a synthesis method of high-purity porous γ-Al2O3 catalyst possessing high efficiency with abundant pore structures. In this paper, based on the chemistryof hydrolysis condensation reaction of aluminum alkoxide, mesoporous γ-Al2O3 microspheres with high surface area, pore volume and purity were synthesized under normal temperature and pressure conditions, and the influences of additive dosage, reaction temperature, post-treatment drying temperature and other factors on the pore structure and morphology of γ-Al2O3 were also systematically studied. In the same breath, the supported mesoporous Pd/γ-Al2O3 microsphere catalytic material with highly dispersed precious metal Pd was further prepared by the impregnation method, which clearly performed excellent catalytic performances in both hydrogenation of nitrobenzene and oxidation of benzyl alcohol. Due to the abundant mesoporous pore structure and highly dispersed loaded precious metal Pd, the mesoporous Pd/γ-Al2O3 microspheres achieved 93.78% nitrobenzene conversion and 98.58% aniline selectivity after 30 min, which are respectively 15.55% and 17.58% higher than that of the commercial nanoparticle Pd/γ-Al2O3, the catalytic performance remained essentially unchanged after recycling. The benzyl alcohol conversion realized a remarkable increase of 26.39% compared to the comparison sample and remained unchanged in a long time oxidation reaction of benzyl alcohol. This work will provide a new strategy for developing high-performance porous γ-Al2O3 loaded catalysts.

    Dynamic Amorphous Photonic Structure Patterns Assembled by Hexagonal Magnetic Nanosheets
    LI Lin, QI Fenglian, QIU Lili, MENG Zihui
    2022, 43(8):  20220123.  doi:10.7503/cjcu20220123
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    Hexagonal Fe2O3 nanosheets were firstly prepared by a high-temperature solvothermal method. Then, a modified St?ber method was employed to coat Fe2O3 nanosheet with a SiO2 shell, following with a gas-phase reduction method for the preparation of the monodisperse hexagonal Fe@SiO2 nanosheet(FeNSs). The obtained FeNS with the total side thickness of 220 nm and the total diagonal length of 400 nm has the advantages of uniform sizes, good dispersity and anisotropy. Notably, the FeNS was ferromagnetic with the saturation magnetization of 25.7 A·m2·kg-1. Serving as building blocks, FeNSs assembled to a novel amorphous photonic structure(APS) under the synergistic effect of the magnetically induced force, evaporation-induced capillary force and mechanical force. By tuning the angle of magnetic fields from 0° to 80°and 90°(relative to the plane of substrates), the chromatic APS patterns with red, green and purple was obtained, respectively. From the characterization of SEM and FFT, it is demonstrated that the assembly of APS is mainly attributed to the magnetically induced control of the long axis of FeNSs. Additionally, by using the dependence of the structural color of APS on the magnetic field orientation, various APS patterns with dynamic structural colors were also obtained.

    Analytical Chemistry
    A Ratiometric Electrochemical Sensor Based on Silver Ion Interaction with DNA for the Detection of Silver Ion
    LI Yulong, XIE Fating, GUAN Yan, LIU Jiali, ZHANG Guiqun, YAO Chao, YANG Tong, YANG Yunhui, HU Rong
    2022, 43(8):  20220202.  doi:10.7503/cjcu20220202
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    A ratiometric electrochemical sensor for detecting silver ion(Ag+) is proposed. Single-stranded DNA labeled with chromium metal organic framework(Cr-MIL-101 NH2) is used as a signal probe(Cr-MOFs-SP), and ferrocene formic acid in the electrolyte solution is used as an internal reference probe(Fc-RP). In the presence of Ag+, the signal of Cr-MOFs can be detected. At the same time, the signal of ferrocene formic acid remained stable. Therefore, the Ag+ concentration can be monitored by the ratiometric response of ICr-MOFs-SP/IFc-RP. The proposed ratiometric biosensor can effectively eliminate the influence of the external environment and avoid electrochemical background signals, also improve the reproducibility, accuracy and sensitivity of detection. The DNA tetrahedral nanomaterials(NTH) with a three-dimensional structure can effectively eliminate the non-specific adsorption of DNA. The well-designed DNA NTH enhances mechanical rigidity, can increase the capture amount of Ag+ and the load of signal substances, and further improve the detection sensitivity. This ratiometric biosensor has a good selectivity for Ag+ detection, a wide linear range(0.1—100 nmol/L) and a low detection limit(33 pmol/L). This sensor has been used for the determination of Ag+ content in Dianchi Lake water samples with the recovery rate of 96.8%—103.0%, which shows that this sensor has potential practical application prospects.

    Fabrication of a Dispersible Large-sized Graphene Quantum Dot Assemblies from Graphene Oxide and Its Electrogenerated Chemiluminescence Behaviors
    WANG Ruina, SUN Ruifen, ZHONG Tianhua, CHI Yuwu
    2022, 43(8):  20220161.  doi:10.7503/cjcu20220161
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    A dispersible large-sized graphene quantum dots assemblies(LSGQD-NAs) in aqueous solution with strong electrochemiluminescence activity was fabricated from graphene oxide by nitric acid etching. LSGQD-NAs were characterized by transmission electron microscopy(TEM), atomic force microscopy(AFM), Fourier transform infrared spectroscopy(FTIR) and Raman spectroscopy(Raman), etc. The results demonstrated that the large-sized graphene quantum dots had an average height of 20 nm and contained abundant carboxyl and hydroxyl groups. Strong ECL was studied in detail with the coreaction of K2S2O8 and the maximum emission wavelength at 685 nm. It is found that LSGQD-NAs can be easily assembled and modified on the surface of GC electrode through the π?π bond action of unoxidized graphene. This study provides a new method for the research of ECL sensor based on graphene quantum dots.

    Organic Chemistry
    Template Simulation of Organophosphorus Nerve Agent Molecularly Imprinted Polymers
    WENG Meiqi, SHANG Guiming, WANG Jiatai, LI Shenghua, FAN Zhi, LIN Song, GUO Minjie
    2022, 43(8):  20220136.  doi:10.7503/cjcu20220136
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    We herein firstly present paraoxon(PO) can be alternative to bis(4-nitrophenyl) phosphate(BNPP) as template simulants of organophosphorus nerve agents molecularly imprinted polymers(MIPs). Geometric optimization and frequency computational calculation of template-monomer complexes were carried out by B3LYP-D3(BJ)/6-31G(dp) level of DFT theory. The configuration stability and binding energy of the complexes formed by both BNPP and PO with various functional monomers were compared and discussed in detail. And it was confirmed that the bifunctional monomer system composed of 4-methylacrylamide antipyrine(MAAP) and methacrylic acid(MAA) were the optimum monomers in this study. Then the core-shell MIPs of SiO2@BNPP were prepared by the surface molecular imprinting technology with BNPP as template molecule, MAAP-MAA as monomers, ethylene glycol dimethacrylate(EGDMA) as crosslinker, and silica nanoparticles as supports. The surface morphology of MIPs was analyzed with SEM and TEM, and then the adsorption properties of the MIPs were measured. The results showed that the maximum absorption capacity of the derived MIPs to BNPP template was 19.03 mg/g when n(BNPP)/n(MAAP)/n(MAA)/ n(EGDMA) was 1∶1∶4∶20. The separation coefficient of MIPs to 4-nitrophenol(4-NP) was 17.50. Furthermore, MIPs had rapid adsorption ability to the BNPP templates, which could reach 92% of the adsorption equilibrium in 5 min, and the adsorption equilibrium time was only 15 min. The MIPs still maintained good reusability after 5 times of reuse. The adsorption process of MIPs to the template was appropriately described by pseudo second-order kinetic model and Langmuir isothermal adsorption equation. Scatchard equation analysis showed that MIPs had two classes of adsorption sites. The consistency between the experimental results and the computational simulation shows that the computational calculation simulation is helpful for the design of organophosphorus nerve agent MIPs.

    Silver-catalyzed 5+1 Cyclization of 2-Vinylanilines with Benzisoxazoles
    GE Yicong, NIE Wanli, SUN Guofeng, CHEN Jiaxuan, TIAN Chong
    2022, 43(8):  20220142.  doi:10.7503/cjcu20220142
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    A novel and facile silver-catalyzed [5+1] annulation reaction between 2-vinylanilines with benzisoxazoles was developed, resulting in the rapid formation of structurally diversified 2-quinolinylaniline derivatives containing NN-bidentate chelating skeleton in moderate to excellent yields. This protocol features broad substrate scope, high atom-economy, mild reaction conditions and so forth, which provides a new idea for the synthesis of NN-bidentate chelating molecules widely used.

    Bio-chemical Synthesis of Melanin Precursor—— 5,6-Dihydroxyindole(DHI)
    JIN Ruiming, MU Xiaoqing, XU Yan
    2022, 43(8):  20220134.  doi:10.7503/cjcu20220134
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    In this study, the biological oxidation step for the synthesis of dopachrome(DC) from L-3,4-dihydroxyphenylalanine(L-Dopa) catalyzed by Saccharomyces cerevisiae BY4741/pYX212-TYR and the chemical step for the reductive synthesis of 5,6-dihydroxyindole(DHI) from DC were coupled, realizing the bio-chemical synthesis of DHI. By optimizing the reaction conditions and the oxygen supply strategy of the biological oxidation step, the conversion rate of L-Dopa increased to 94.75%; by optimizing the reaction conditions and chemical additives of the chemical reduction step, the yield of DHI increased to 90.03%. Ultra high performance liquid chromatography tandem quadrupole time of flight mass spectroscopy(UPLC-Q-TOF-MS) identification for the products showed that DHI-soluble oligomers existed in the reaction system.

    Physical Chemistry
    Organocatalytic Enantioselective Mannich-type Addition of 5H-Oxazol-4-ones to Isatin Derived Ketimines
    HUANG Qiuhong, LI Wenjun, LI Xin
    2022, 43(8):  20220131.  doi:10.7503/cjcu20220131
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    Chiral 3,3′-disubstituted oxindoles are widely present in a variety of natural products and bioactive molecules. And the nature of substituents and the absolute configuration of the stereo center at the C3 position have a great effect on the bioactivities of these chiral oxindoles. Therefore, it is of great significance to develop efficient and practical methods to construct chiral 3,3′-disubstituted oxindole compounds. In particular, the enantioselective Mannich-type addition of isatin derived imines is one of the most straightforward method for forging chiral 3,3′-disubstituted oxindole compounds. Based on previous experiments, it was found that the 5H-oxazol-4-ones, which had diverse reactive sites and could be easily converted into important α-alkyl-α-hydroxy derivatives, were potential candidate nucleophile for enantioselective Mannich-type addition reaction. Herein, we reported the first chiral phosphoric acid catalyzed enantioselective Mannich-type addition reaction of isatin derived ketimines with 5H-oxazol-4-ones. Various of electron-withdrawing or electron-donating substituted isatin derived ketimines and 5H-oxazol-4-ones. Various of electron-withdrawing or electron-donating substituted isatin derived ketimines and 5H-oxazol-4-ones could be better adapt to the reaction conditions to construct chiral 3,3′-disubstituted oxindole compounds with good to excellent yields(up to 97%), enantioselectivities(up to 99% e.e.) and diastereoselectivities(all>20∶1 d.r.). What’s more, the reaction could be scaled up, and the synthetic utility of the desired chiral 3,3′-disubstituted oxindoles was proved by transformations.

    Density-functional Theoretical Study on the Interaction of Indium Oxyhydroxide Clusters with Carbon Dioxide and Methane
    HE Hongrui, XIA Wensheng, ZHANG Qinghong, WAN Huilin
    2022, 43(8):  20220196.  doi:10.7503/cjcu20220196
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    Both carbon dioxide(CO2) and methane(CH4) as fossil energy gas fuel are chemically stable molecules with a large greenhouse effect, so it is theoretical and practical significance to investigate their activation, transformation and utilization. The density functional theory(DFT) method were used to investigate computationally the interaction of indium oxide clusters with CO2, CH4 and CO2+CH4. The results show that, indium oxide clusters activate CO2 and CH4via —In—O(bridge)— with [2+2] addition mode, and the presence of hydroxyl changes the local charge of the active site of indium oxide clusters, leading to significantly decrease of activation free barrier for their interaction with CO2 and CH4, and then making the activation be easily proceeded. Interestingly, the difference of local charges between In and O(qInqO) of the active site —In—O— correlates well with the activation of CO2 and CH4i.e., the greater the qInqO, the lowest the activation free barrier for their interaction with CO2 and CH4. For activation of CO2 and CH4 by indium oxyhydroxide clusters, electrons transfer to CO2 and CH4 from the clusters(nucleophilic activation), and for that by indium oxide clusters without hydroxyl, the opposite transfer of electrons occurs(electrophilic activation).

    Effects of 5,5-Dimethylhydantoin on Electroless Copper Plating
    ZHENG Anni, JIN Lei, YANG Jiaqiang, WANG Zhaoyun, LI Weiqing, YANG Fangzu, ZHAN Dongping, TIAN Zhongqun
    2022, 43(8):  20220191.  doi:10.7503/cjcu20220191
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    In this paper, the effects of 5,5-dimethylhydantoin(DMH) on electroless copper plating were studied in the solution containing sodium potassium tartrate and disodium ethylene diamine tetraacetic acid as the complexing agents, and formaldehyde as the reducing agent. The experimental results of the electroless copper plating show that DMH can improve the stability of the bath. SEM and appearance images show that DMH can reduce the particle size of the copper coating and make the coating brighter and more compact. UV-Vis absorption spectra reveal that DMH does not strongly coordinate with Cu(II) in the bath. Linear voltammetry curves illuminate that DMH can inhibit the generation of Cu+ ions or promote the reduction of Cu+ ions, and reduce the oxidation rate of the formaldehyde during electroless copper plating. XRD patterns show that the copper coatings obtained from the baths both with and without DMH present the same face-centered cubic multi-crystal structures. No Cu2O diffraction peak is detected.

    Lithium Polystyrene Sulfonate Based Interfacial Protective Layer for Lithium Metal Anodes
    LI Wei, LUO Piao, HUANG Lianzhan, CUI Zhiming
    2022, 43(8):  20220166.  doi:10.7503/cjcu20220166
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    Due to the ultrahigh theoretical specific capacity(3860 mA·h/g) and lowest negative electrochemical potential[?3.04 V(vs. SHE)], lithium metal has long been considered as an ideal anode for next-generation high- energy-density lithium batteries. However, several critical issues such as volume expansion, lithium dendrite, and side reaction have restricted its practical application. Here, lithium polystyrene sulfonic(PSSLi) was evenly coated on the surface of commercial lithium metal foil to form the PSSLi@Li composite electrode. Fourier transform infrared spectroscopy(FTIR), electrochemical impedance(EIS), battery performance test and finite-element-based solver simulation were used to analyze the physical and electrochemical properties of this composite anode. The results indicated the PSSLi layer can effectively avoid the side reaction between electrolyte and Li metal, restricting the formation of "dead Li". In addition, PSSLi with the neatly arranged sulfonic groups can homogenize the Li ions flux and distribution on the electrode surface, which ensures the uniform plating/stripping of Li metal. The electrochemical test showed that the coulombic efficiency of the PSSLi@Cu composite electrode can remain above 99.5% after 350 cycles. And the symmetrical cell assembled with PSSLi@Li composite electrodes presents an excellent cycling life over 1200 h under the current density of 1 mA/cm2 and area capacity of 1 mA·h/cm2. Moreover, the LiFePO4(LFP) coupled full cell can maintain at 115 mA·h/g under the rate of 1C after 500 cycles and realize an ideal capacity retention(81%). The full cell also exhibits an excellent rate performance of 105 mA·h/g at the rate of 8C.

    Enhance of CoSe2/C Composites Modified Separator on Electrochemical Performance of Li-S Batteries at High Sulfur Loading
    HAN Fuchao, LI Fujin, CHEN Liang, HE Leiyi, JIANG Yunan, XU Shoudong, ZHANG Ding, QI Lu
    2022, 43(8):  20220163.  doi:10.7503/cjcu20220163
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    Herein, CoSe2/C composite was obtained by a simple two-step calcining method with the rhombohedral dodecahedral ZIF-67 as the template. The CoSe2 nanoparticles with diameters of approximately 30 nm were dispersed in the carbon skeleton maintaining the structure of the template. Systematically electrochemical results demonstrated that the CoSe2/C composite could fasten the kinetics of the soluble lithium polysulfides, as well as guide the deposition of the insoluble Li2S during the discharge process. In addition, the CoSe2/C could also boost the oxidation of Li2S. It was loaded on commercial Celgard 2400 separators as the electrocatalytic materials. It is worth to note that the mass loading of the modified layer is only 0.15 mg/cm2, in which the CoSe2/C composite only accounts for 30%(mass fraction). Consequently, the cells with CoSe2/C-modified separator delivered a superior electrochemical performance, which with a high sulfur loading of 4.8 mg/cm2 gave an initial specific capacity of 756 mA·h/g at 0.2C and maintained at 715 mA·h/g after 180 cycles, with a capacity decay rate of 0.031% per cycle.

    Preparation and Lithium Storage Performance of Pseudocapacitance-controlled Perovskite High-entropy Oxide La(Co0.2Cr0.2Fe0.2Mn0.2Ni0.2)O3 Anode Materials
    JIA Yanggang, SHAO Xia, CHENG Jie, WANG Pengpeng, MAO Aiqin
    2022, 43(8):  20220157.  doi:10.7503/cjcu20220157
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    La(Co0.2Cr0.2Fe0.2Mn0.2Ni0.2)O3 high-entropy oxide(HEO) was prepared by co-precipitation using metal nitrate as the metal source, NaOH and Na2CO3 as the precipitant and explored as a novel anode active material for lithium-ion batteries(LIBs). The microstructure and electrochemical properties of as-synthesized La(Co0.2Cr0.2Fe0.2Mn0.2Ni0.2)O3 HEO were investigated and also compared with conventional LaCoO3. Scanning electron microscopy(SEM), X-ray diffraction(XRD) and N2 adsorption/desorption tests showed that the as-prepared La(Co0.2Cr0.2Fe0.2Mn0.2Ni0.2)O3 HEO was a single-phase perovskite structure, and spherical shape with chemical and microstructural homogeneity, and high specific surface area(19.83 m2/g). As compared to conventional LaCoO3, the La(Co0.2Cr0.2Fe0.2Mn0.2Ni0.2)O3 anode material not only provides the higher specific capacity, but also exhibits excellent rate performance and cycling stability. The initial discharge specific capacity of La(Co0.2Cr0.2Fe0.2Mn0.2Ni0.2)O3 anode is 855.8 mA·h/g at the current density of 200 mA/g, and after 150 cycles, the specific capacity increases to 771.8 mA·h/g, which is much higher than the theoretical capacity(331.6 mA·h/g). It is worth noting that La(Co0.2Cr0.2Fe0.2Mn0.2Ni0.2)O3 anode delivers the specific capacitity of 320 mA·h/g at 3000 mA/g with a capacity retention rate of 95.1% after 500 cycles, which is close to its theoretical capacity. The improved lithium storage performance of La(Co0.2Cr0.2Fe0.2Mn0.2Ni0.2)O3 is mainly attributed to the entropy-stabilized crystal structure and the multiprincipal synergistic effect, resulting in the improved lithium ion diffusion coefficient(11.2×10-18 cm2/s) and pseudocapacitance contribution.

    Construction of Mn-Cu Bimetal Containing Phyllosilicate Nanozyme and Evaluation of the Enzyme-like Properties
    HE Beibei, YANG Kuihua, LYU Rui
    2022, 43(8):  20220150.  doi:10.7503/cjcu20220150
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    A Mn-Cu containing bimetallic phyllosilicate(AMCP) was prepared by one-pot sol-gel method, which was verified to present intrinsic laccase-like and peroxidase-like performance. The results indicated that AMCP presented a well confined 2-dimentional layered structure, and the varied valence states arose from Mn and Cu endow it with excellent enzyme-mimetic activities. Moreover, it exhibits superior pH and temperature tolerance comparing with natural analogue, when the temperature was higher than 70 ℃, AMCP retained above 80% activity while natural enzyme was completely deactivated. Besides, it also remained around 90% activity under pH value of 3—9. Finally, the catalytic mechanism indicated the electron transfer between Mn and Cu accelerated the cycle of Cu2+ and Cu+, which could promote the production of ROS and facilitate the catalytic performance of AMCP. This work provides a novel strategy and direction for the customization of high performance, multi-enzyme mimetic nanozyme, which has a potential application prospect on biosensing, disease therapy and environmental remediation.

    Effects of Amine Structures on the pH Window of Oleic Acid Vesicle
    LI Lei, FANG Yun, XIA Yongmei, FAN Mengqi, FAN Ye
    2022, 43(8):  20220144.  doi:10.7503/cjcu20220144
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    The pH window of oleic acid vesicle(OAV) was defined by laser Tyntall effect and turbidity observation, and effects of amine structure on the pH window were investigated involving in spacer lengths of diamines, numbers of amino groups in polyamines, alkyl chain lengths of primary fatty amines and quaternization. It is found that diamines and polyamines could mostly extend the pH window of OAV into the alkaline region, while primary fatty amines and dodecyltrimethylammonium bromide(DTAB) could result in a new metastable to stable vesicular phase at the low pH region besides the above window extension. Regulation of the pH window of OAV driven by amines is generally relying on transformation between protonation and deprotonation of amino groups under different pH, while cooperating with hydrophobic interaction of fatty amines or electrostatic attraction of DTAB. Thermodynamic parameters for molecular interactions and binding energy calculation show that the non-covalent bonding of diethyle-netriamine, as a representative of diamines or polyamines, with the OAV surface is dominated by hydrogen bond or ion-dipole interaction, which has weaker effect on the pH window of OAV than the hydrophobic co-assembly with primary fatty amines or electrostatic attraction with DTAB.

    CO2 Absorption in Composite of Aprotic Solvent and Iron-based Ionic Liquid
    CUI Wei, ZHAO Deyin, BAI Wenxuan, ZHANG Xiaodong, YU Jiang
    2022, 43(8):  20220120.  doi:10.7503/cjcu20220120
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    Two kinds of aprotic solvents, polyethylene glycol dimethyl ether(NHD) and NN-dimethylacetamide (DMAC), which have excellent desulphurization and decarbonization ability, were selected to construct composite of BmimFeCl4 and solvent as novel decarbonization agents. The effects of temperature, mass ratio of BmimFeCl4/solvent and pressure on CO2 solubility were investigated. The results show that high pressure and low temperature are more conducive to the dissolution of CO2. The Henry coefficient of BmimFeCl4/DMAC(7∶3) with 0.9181 MPa·L·mol-1 at 298.2 K, is lower than BmimFeCl4/NHD under the same conditions, indicating that the former has a larger absorption capacity for carbon dioxide. Fourier transform infrared spectroscopy(FTIR) spectra show that the absorptions of carbon dioxide by the two composites depends on physical absorption between CO2 molecule and the functional groups of BmimFeCl4 before and after CO2 absorption. After five absorption-regeneration cycles of CO2 with the two kinds of the iron-based ionic liquid composites, the amounts of CO2 absorption reached 92.53% and 99.04% of the first absorption for BmimFeCl4/NHD and BmimFeCl4/DMAC, respectively. density functional theory(DFT) calculations and IRI analyses show that CO2 is more likely to interact with [Bmim]+ cations and DMAC molecules in BmimFeCl4/DMAC, nevertheless, in BmimFeCl4/NHD, CO2 is more likely to interact with [FeCl4- anions and NHD molecules.

    Preparation of Hierarchical Microporous-mesoporous Fe2O3/ZSM-5 Hollow Molecular Sieve Catalytic Materials and Their Catalytic Properties for Benzylation
    YAO Yiting, LYU Jiamin, YU Shen, LIU Zhan, LI Yu, LI Xiaoyun, SU Baolian, CHEN Lihua
    2022, 43(8):  20220090.  doi:10.7503/cjcu20220090
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    As a kind of efficient and environment friendly solid catalyst, ZSM-5 zeolite shows extremely uniform pore structure, excellent shape selectivity, great catalytic activity and superb hydrothermal stability, which has already been used in plenty of fields like petroleum catalytic cracking, fine-chemicals processing and environmental protection. However, its simplex microporous structure severely reduces the diffusion of guest molecules, which results in a great limitation of aromatic alkylation reaction in which macromolecules participate. In this paper, through a method of etching ZSM-5 zeolite with NaOH/TPAOH(tetrapropylammonium hydroxide) mixed alkali, a hierarchical micro-/mesoporous ZSM-5 catalyst with high crystallinity and abundant specific surface area was prepared. This special hierarchical structure can not only maintain the great hydrothermal stability and plentiful active centers of microporous ZSM-5, but also promote the diffusion of reactants and products with the introduction of mesopores. As a result, the conversion of m-trimethylbenzene benzylation increased 3.8 times. In addition, a bifunctional hierarchical micro-/mesoporous Fe2O3/ZSM-5 hollow catalyst was developed by loading Fe on the hierarchical microporous- mesoporous ZSM-5 hollow catalyst mentioned above, which exhibited excellent catalytic performance in the benzylation reaction of benzene, and the conversion, selectivity and percent yield reached 98.3%, 81.6% and 80.2% while Fe loading was 6.67%(mass fraction), and the reaction temperature and the reaction time were 75 ℃ and 15 min, respectively.

    Atomic Scale Investigation of Pt Atoms/clusters Promoted Co-catalyzed Fischer-Tropsch Synthesis
    WEI Chunhong, JIANG Qian, WANG Panpan, JIANG Chengfa, LIU Yuefeng
    2022, 43(8):  20220074.  doi:10.7503/cjcu20220074
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    By utilizing scanning transmission electron microscopy with spherical aberration(AC-STEM), combining with H2-TPR, CO-chemisorption and quasi in situ XAS, we investigated the promotion effect of the noble metal, platinum in cobalt-based Fischer-Tropsch catalysts, and the effect of metal-support interaction was excluded by the use of the chemical inert support, β-SiC. It was concluded that the Pt promoter improved both the dispersion and reduction of cobalt nanoparticles, which increase the amount of Co0 active sites, and therefore facilitate the catalytic performance of Fischer-Tropsch synthesis. With the aid of AC-STEM, it was observed that Pt was in atomic dispersion in the form of single atoms and clusters. According to this structure, we speculated that the promotion effect of Pt followed the H2 dissociation and spillover mechanism. The Pt dispersed on cobalt nanoparticles stimulated the H2 dissociation on the catalyst to a great extent. On one hand, this favored the reduction of cobalt species, on the other hand, it facilitated the H2 activation and hydrogen-associated CO dissociation during Fischer-Tropsch synthesis, and thus enhanced the activity of the catalyst and improved the selectivity of saturated hydrocarbons.

    Polymer Chemistry
    Flocculation of Fillers in Isoprene Rubber and Its Effects on Properties
    ZHANG Zhicai, WANG Yuge, GU Qianqian, LYU Yongpeng, XIAO Jianshu, YIN Yuan, SUN Hongguo, ZHENG Yafang, SUN Zhaoyan
    2022, 43(8):  20220155.  doi:10.7503/cjcu20220155
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    The vulcanization process has a significant impact on the filler flocculation in isoprene rubber and its corresponding properties. By changing the vulcanization temperature and vulcanization time, the flocculation processes of fillers in carbon black, silica, and carbon black/silica mixed filler systems were compared, and the influences on its static and dynamic properties were investigated. In order to analyze the contribution of the chemical crosslinked network to the filler flocculation process, the flocculation processes of crosslinked and uncrosslinked systems with the same process at different temperatures and times were compared. In the crosslinked system, the Payne effect mainly comes from the contribution of the filler network and the chemical crosslinked network, while in the uncrosslinked system, the Payne effect mainly comes from the contribution of the filler network. The results demonstrate that the formation of the chemical crosslinked network limits the flocculation of fillers to a certain extent. Therefore, with the increase of temperature, the Payne effect of the crosslinked system decreases, while the Payne effect of the uncrosslinked system gradually increases or first decreases and then increases. With increasing vulcanization time, the Payne effect for both crosslinked and uncrosslinked systems increases, but the mechanisms are different, which can be ascribed to the formation of chemical crosslinked network for crosslinked system, but the flocculation of fillers for the uncrosslinked system. The flocculation kinetics study of fillers shows that fast flocculation occurs in a short time range, and then changes to slow but will not stop over a long period of time, and the flocculation still occurs even at lower temperatures(60 ℃). In addition, high temperature and prolonged heat-treatment resulted in a decrease in the tensile properties of the material, but an enhancement of the dynamic fatigue properties.

    Gemcitabine/polypyrrole Composite Nanoparticles for Chemo-photothermal Combination Ovarian Cancer Therapy
    LIU Shuwei, JIN Hao, YIN Wanzhong, ZHANG Hao
    2022, 43(8):  20220345.  doi:10.7503/cjcu20220345
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    Polypyrrole nanoparticles(NPs) were prepared through iron ion-induced oxidative poly?merization and employed for loading chemotherapy drug gemcitabine, thus producing gemcitabine/polypyrrole composite NPs. The composite NPs indicate strong loading capacity for gemcitabine and good stability in aqueous solution, which reduces the toxicity and side effects of gemcitabine on normal tissues. In addition, the composite NPs have strong absorption in the near-infrared region and can transform the absorbed light energy into heat, acting as an efficient photothermal reagent for tumor photothermal therapy. Meanwhile, the composite NPs are capable to release gemcitabine and perform photothermal-guided chemotherapy. As the reagent with chemo-photothermal combination therapeutic efficacy, gemcitabine/polypyrrole composite NPs can ablate ovarian cancer cells under near-infrared laser irradiation, showing the potential for ovarian cancer therapy.

    Preparation and High Temperature Fuel Cell Performance of Ionic Crosslinked Sulfonated Polyimides for Proton Exchange Membranes
    QIU Xinsheng, WU Qin, SHI Daxin, ZHANG Yaoyuan, CHEN Kangcheng, LI Hansheng
    2022, 43(8):  20220140.  doi:10.7503/cjcu20220140
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    A series of ionic crosslinked sulfonated polyimide based proton exchange membranes(SPI PEMs) was prepared by casting method after copolymerization of 2,2′-bis(4-sulfophenoxy) benzenediamine, 2-(4-aminophenyl)-5-aminobenzimidazole and 1,4,5,8-naphthalenetetracarbo-xylic dianhydride. The ionic crosslinked SPI PEMs show excellent mechanical properties and water stability. Those with high ion exchange capacity(IEC) show comparable proton conductivity to NR212 when under high relative humidity. The ionic crosslinked SPI PEM(coded by M1) prepared with n(BSPOB)/n(DABI) of 5/2 shows good fuel cell performance with the maximum power output(Wmax) of 0.93 W/cm2 under cell temperature of 90 ℃ and humidification of 80% relative humidity(RH), which is higher than NR212 with Wmax of 0.86 W/cm2. The cell performance largely decreases when cell temperature is up to 110 ℃ for all these PEMs. M1 shows relative high performance with the Wmax of 0.54 W/cm2 at 110 ℃, when compared to covalent crosslinked SPIs. The ionic crosslinked SPI PEM shows about 10% decrease of open circuit voltage(OCV) durability for 300 h under 110 ℃, which is much better than NR212.

    Preparation of Photo/reduction Dual-responsive Hydrogel Microspheres and Their Application in Three-dimensional Cell Culture
    WANG Xuebin, XUE Yuan, MAO Hua’nyu, XIANG Yanxin, BAO Chunyan
    2022, 43(8):  20220116.  doi:10.7503/cjcu20220116
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    A kind of photo/reduction dual-responsive hydrogel microsphere was designed and prepared to achieve scalable three-dimensional(3D) cell culture and enzyme free harvest under mild conditions. The hydrogel microsphere contains a dual-responsive functional monomer(M1), in which the functional groups of ortho-nitrobenzyl ester can ligate with amino compounds under ultraviolet(UV) irradiation, thus achieving effective immobilization of adhesive proteins on the surface of hydrogel microspheres and mediating cell adhesion through protein-integrin interaction. After the growth and proliferation of cells on the surface of microspheres, the disulfide bond group can be reduced by glutathione, which mediates the non-enzymatic and non-destructive release of cells. Such a novel method that regulates cell adhesion and release by immobilization and release of bioactive molecules on the surface of hydrogel microspheres provides a universal and effective strategy for cell engineering.

    Preparation of Composite Semiconductor Micro-sheets with UV Shielding Performance and Its Application in Polypropylene
    JIANG Shenghan, CAO Changlin, XIAO Liren, YANG Tang, QIAN Qingrong, CHEN Qinghua
    2022, 43(8):  20220071.  doi:10.7503/cjcu20220071
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    In order to improve the aging resistance of polypropylene(PP), Mica/MnO2/TiO2 composite semiconductor microsheet was synthesized by chemical liquid deposition method. Then, the microsheets were introduced into PP by physical blending method. The morphology, crystal structure and UV absorption properties were characterized by scanning electron microscopy(SEM), X-ray diffraction(XRD), Raman spectroscopy(RS), UV-Vis diffuse reflection spectroscopy(UV-Vis DRS) and electronic universal testing. The influence of TiO2 contents, concentrations of MnO2 and pH values on the morphology structure, UV shielding performance of microsheet and the anti-aging modification effect of the microsheet on PP were investigated. The results showed that the crystal type of TiO2 in the microsheet could be transformed from anatase to rutile when the addition level of MnO2 was 2.0%, the supporting amount of TiO2 was 20%, and the pH value was 1.6. The microsheet had good coating condition and excellent UV shield performance. Compared with pure PP, after UV aging for 27 d, the amount of C=O produced by PP modified by composite semiconductor microsheet decreased, the surface morphology retention was higher. The UV aging resistance was significantly improved with a 38% increasing tensile strength retention rate.

    Material Chemistry
    Alkane Grafted Phase Change Azobenzene Materials Based on Low Temperature Heat Release
    GAO Jian, FENG Yiyu, FANG Wenyu, WANG Hui, GE Jing, FENG Wei
    2022, 43(8):  20220146.  doi:10.7503/cjcu20220146
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    Alkyl-grafted phase change azobenzenes, 4-pentyl-azobenzene(Azo5) and 2'-methyl-4-n-pentylazobenzene(AzoM5), with two different substituents were synthesized by the Mills method. The chemical structures of Azo5 and AzoM5 were characterized by nuclear magnetic resonance hydrogen spectroscopy and Fourier transform infrared spectroscopy. The isomerization performance, cycling stability, thermal storage, exothermic properties and the ability to release heat at ?10 ℃ of the materials were analyzed by ultraviolet-visible spectroscopy, differential scanning calorimetry and infrared thermography. The results show that Azo5 and AzoM5 exhibit low melting point and rapid isomerization transformation due to the low intermolecular force. And due to the photo-induced phase change at low temperature, the energy density increases significantly, reaching 216 and 218 J/g, respectively. Infrared thermography shows that Azo5 can achieve a temperature increase of 6 ℃ at low temperatures(-10 ℃) under visible light irradiation.