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Table of Content

    10 August 2021, Volume 42 Issue 8
    Contents
    Cover and Content of Chemical Journal of Chinese Universities Vol.42 No.8(2021)
    2021, 42(8):  1-10. 
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    Review
    Recent Advances in Lanthanide Doped Upconversion Nanoparticle-Metal Organic Framework Composites
    WEI Minmin, YUAN Ze, LU Min, MA Hui, XIE Xiaoji, HUANG Ling
    2021, 42(8):  2313-2323.  doi:10.7503/cjcu20210109
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    Lanthanide doped upconversion nanoparticle-metal organic framework composites recently emerge as a new type of functional composites. The composites possess the merits of both lanthanide doped upconversion nanoparticles and metal organic frameworks, exhibit synergistic effects, and holds several advantages, including flexible design and easy functionalization. Herein, we focus on recent advances in the lanthanide doped upconversion nanoparticle-metal organic framework composites. We first review the synthetic strategies of the composites, and then discuss representative applications of the composites in diverse fields, such as biology and catalysis. We also envision the challenges and perspectives on the future development of the lanthanide doped upconversion nanoparticle-metal organic framework composites.

    Applications of Bifunctional Biaryl-2-ylphosphine Ligands in Asymmetric Gold Catalysis
    ZHAO Ke, HONG Zhi, ZHANG Liming
    2021, 42(8):  2324-2331.  doi:10.7503/cjcu20210169
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    Homogeneous asymmetric gold catalysis had experienced remarkable development since 2005 and been applied extensively in organic synthesis. In the past several years, the development of chiral functiona-lized biaryl-2-ylphosphine ligands opens new approaches to achieving asymmetric gold catalysis. This review summarizes several advances in this area and highlights the enabling interactions such as H-bonding, acid-base interaction, coulombic attraction, and π-π stacking between ligand functional groups and substrates in asymmetric induction.

    Progress of Key Electronic States in Lithium Ion Battery Materials Probed Through Soft X-ray Spectroscopy
    ZHUO Zengqing, PAN Feng
    2021, 42(8):  2332-2341.  doi:10.7503/cjcu20210232
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    The formidable challenges for developing high energy/power density, low cost, and safe lithium ion battery have necessitated employing advanced tools to understand the intrinsic physical and chemical pro-perties of battery materials. Electronic structure of batteries materials determines the electrochemical performance, e.g., the potential and sequence of cationic and anionic redox, the voltage and capacity decay mechanism upon electrochemical cycling. It is crucial to detect and control the electronic state evolution of battery materials through advanced experimental characterizations. Synchrotron based soft X-ray spectroscopy stands out as one of the most effective way directly measuring both the occupied and unoccupied states in the vicinity of Fermi level, which is relevant to battery comprehensive performance. As core level spectroscopies, soft X-ray spectroscopy provides direct probe of the relevant transition-metal(TM) 3d states and anion p states in battery materials with elemental, chemical, and orbital sensitivity through excitation from core state to shallow unoccupied state. Quantitative analysis of TM L-edge and anion K-edge soft X-ray spectroscopy provides detailed information about local structural effects, valence, and spin states of battery materials. In this work, we review the soft X-ray spectroscopy of the evolution of electronic state in battery materials. We start with an overview of the main experimental aspects of soft X-ray spectroscopy. We subsequently discuss both cationic and anionic redox in battery materials through soft X-ray spectroscopy, which is meaningful in practice for enhancing the performance of a battery. The recently developed mapping of resonant inelastic X-ray scattering(mRIXS) is a powerful probe of battery chemistry with superior sensitivity. The mRIXS is demonstrated as a reliable technique for fingerprinting oxygen redox, and the tool-of-choice to study the fundamental nature of bulk oxygen states.

    Influencing Factors and Promotion Strategies of the First-cycle Coulombic Efficiency of Silicon Suboxide Anodes in Lithium-ion Batteries
    LI Huiyang, ZHU Siying, LI Sha, ZHANG Qiaobao, ZHAO Jinbao, ZHANG Li
    2021, 42(8):  2342-2358.  doi:10.7503/cjcu20210177
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    The popularity of electric vehicles and various portable electronic devices has led to higher demands on battery energy density. Silicon suboxide(SiOx, 0<x≤2) shows high specific capacity and low Li-ion insertion potential, and the volume expansion effect is significantly lower than that of pure silicon anode, and therefore is considered to be one of the ideal alternatives to traditional graphite anode materials. However, the solid electrolyte interphase(SEI) and a large number of irreversible products are formed during the first lithiation/delithiation cycle, resulting in low Coulombic efficiency, which seriously hinders the practical application of SiOx anodes. On the basis of SiOx structure, this review systematically explained the lithium storage mechanism of SiOx anode and the reason for the low first-cycle efficiency. Further, strategies of improving the first Coulombic efficiency of SiOx anode in recent years is summarized in detail. Finally, the future direction of improving the first-cycle efficiency of SiOx anode is also forecasted.

    Research Progress of Flexible Tactile Sensors Applied to Wearable Electronics
    PAN Xiaojun, BAO Rongrong, PAN Caofeng
    2021, 42(8):  2359-2373.  doi:10.7503/cjcu20210012
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    The flexible tactile sensor is a type of device that imitates the human tactile. It can get the information and data of the human body and the external environment. The application in medical detection and intelligent robots provides a broad prospect. Recently, many researches have greatly improved the performance of flexible tactile sensors. In the first part of this review, the structure and basic performance of flexible tactile sensors is introduced. In the second part, we discuss a new type of tactile sensor with self-healing, self-driving and visualization. The third part discusses the application of flexible tactile sensors in wearable electronic technology, medical care and human-computer interaction interface. The final part of the article discusses the challenges that flexible tactile sensors will face in the future.

    Inorganic Chemistry
    Fabrication and Optical Mechanism of Plasmonic Nanodimer with Uniform Orientation
    WANG Zhaoyi, MU Shilin, ZHANG Xuemin, ZHANG Junhu
    2021, 42(8):  2374-2380.  doi:10.7503/cjcu20210289
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    Vertically stacked plasmonic dimers were succussfully fabricated by step-by-step evaporation of Au, SiO2 and Au(or Ag) with monolayer colloidal spheres mask followed by annealing treatment. The novel method offers sufficient degree of freedom to construct both homo- and hetero- plasmonic dimers with the same orientation over a macroscopic scale. Hybridization between the plasmon modes of the top and bottom nanoparticle was clearly observed. As the hybridization between nanoparticles was orientationally dependent, the vertically stacked nanoparticle dimers exhibited a unique angular dependent extinction property. Moreover, the difference of optical property between Au/SiO2/Au homo-dimers and Au/SiO2/Ag hetero-dimers was discussed. In contrast with Au/SiO2/Au homo-dimers, Fano profiles are present in Au/SiO2/Ag hetero-dimers due to the coupling between Ag dipole plasmon mode and Au interband absorption. This work offer a versatile strategy to tune the location, strength, as well as line shape of optical resonances of noble metallic nanoparticles. We believe that the plasmonic dimers obtained have both experimental and theoretical potentials in the nanophotonics realm.

    Controllable Growth of Silver Nanoparticles on TiO2 Tetragonal Prism Nanarrays and Its SERS Effect
    CHEN Shaoyun, ZHANG Xingying, LIU Ben, TIAN Du, LI Qi, CHEN Fang, HU Chenglong, CHEN Jian
    2021, 42(8):  2381-2392.  doi:10.7503/cjcu20210005
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    The TiO2 tetragonal prism array structure was deposited on the conductive surface of the conductive glass FTO by hydrothermal method. The silver nanoparticles(AgNPs) grew on the TiO2 tetragonal prism by polyvinylpyrrolidone(PVP) reduced Tollens reagent to form TiO2@AgNPs-PVP micro-nano structure, while the silver nanoparticles grew on the TiO2 tetragonal prismby trisodium citrate(TSC) reduced silver nitrate to form TiO2@AgNPs-TSC micro-nano structure. The as-prepared micro-nano structures could be used as the substrate for surface enhanced Raman scattering(SERS). The results showed that the size and distribution of Ag NPs nanoparticles on the TiO2 tetragonal prism array could be adjusted by the concentration of Tollens reagent and the reaction time of TSC to optimize the SERS substrate. The detection limits of the optimized TiO2@AgNPs-PVP substrate for rhodamine 6G(R6G) and melamine are 10-12 mol/L and 0.01 mg/mL, respectively. The optimized TiO2@AgNPs-TSC micro-nano structure for R6G and melamine are 10-10 mol/L and 0.01 mg/mL, respectively. In addition, the SERS activity and recyclability of TiO2@AgNPs-PVP and TiO2@AgNPs-TSC substrates were closely related to the types of reducing agents: the PVP coated on Ag nanoparticles could be used as an isolation layer to avoid direct contact with nanoparticles, which could prevent the quenching of electromagnetic field coupling to enhance the SERS activity of the substrate. However, the adsorbed small molecules(such as R6G) could not be cleaned when the TiO2@AgNPs-PVP was used as a recyclable SERS substrate. It was attributed to the fact that the PVP was a water-based polymer with strong hydrophilicity.

    Analytical Chemistry
    Preparation of Paper Hollow Gold Nanocage SERS Sensor and Its Rapid and Highly Sensitive Detection for miRNAs in Sputum of Patients with Non-small Cell Lung Cancer
    XUE Jin, CAO Xiaowei, LIU Yifan, WANG Min
    2021, 42(8):  2393-2402.  doi:10.7503/cjcu20210280
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    The abnormal expression of nucleic acid is closely related to the occurrence and development of tumor. Detecting the expression of micro-RNA(miRNAs) markers is of great significance for the diagnosis and treatment of non-small cell lung cancer(NSCLC). In this work, the monolayer hollow gold nanocages(HGNCs) array substrate was fabricated by the self-assembly method at the oil-water interface. It was proved that the HGNCs gap provided a large number of “hot spots” by FDTD method, which made the substrate exhibit an excellent surface-enhanced Raman scattering(SERS) performance. At the same time, the hairpin DNA labeled by Raman signal molecule was linked with the substrate, and then the SERS signal was detected after complementary hybridization with the target miRNAs. The detection limits of miR-196a and miR-21 in sputum were 10.00 and 36.15 amol/L, respectively. In order to verify the accuracy of the sensor in clinical detection, the SERS sensor was used to detect miR-196a and miR-21 in sputum of patients with NSCLC, and the results were compared with those of real-time quantitative polynucleotide chain reaction technology. There were no significant differences between the results of the two detection methods, which both showed that the expressions of miR-196a and miR-21 in sputum of NSCLC patients were higher than those of healthy people, and the relative standard deviations were less than 10%. Therefore, the paper HGNCs SERS sensor has potential application in NSCLC diagnosis, and may become an alternative tool for miRNAs research in biomedical diagnosis field.

    ON-OFF-ON Double Colorimetric and Fluorescent Probes Based on Phenanthro[9,10-d]imidazole Derivatives and Their Living Cells Imaging
    LI Anran, ZHAO Bing, KAN Wei, SONG Tianshu, KONG Xiangdong, BU Fanqiang, SUN Li, YIN Guangming, WANG Liyan
    2021, 42(8):  2403-2411.  doi:10.7503/cjcu20210089
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    The symmetric fluorescent probe PIP-ph-PIP based on phenanthro[9,10-d]imidazole was designed and synthesized, and its structure was characterized and confirmed. As the increasing amount of water in the solution of PIP-ph-PIP, the fluorescence intensity of PIP-ph-PIP first increased and then quenched with the gradual aggregation. The results of the fluorescence spectra indicated that the probe PIP-ph-PIP could selectively and successively recognize Ag+ and SCN-, Cu2+ and PO34 -, respectively, with an ON-OFF-ON mode in the aqueous system. Moreover, the continuous effect can be observed by the colorimetric naked eye. The probe PIP-ph-PIP offered a relatively low detection limits of 6.1 nmol/L for Ag+ ions. The probe PIP-ph-PIP was successfully applied to detect Ag+ and Cu2+ in living human cancer cells(HeLa cells) and quantitively analyze of Ag+ and Cu2+ in actual water samples.

    Efficient Determination of Alkaline Phosphatase Activity Based on Graphene Quantum Dots Fluorescent Probes
    HUANG Shan, YAO Jiandong, NING Gan, XIAO Qi, LIU Yi
    2021, 42(8):  2412-2421.  doi:10.7503/cjcu20210048
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    Based on the static fluorescence quenching effects of benzoquinones on graphene quantum dots(GQDs), a GQDs-based fluorescent probe was established to detect the activity of alkaline phosphatase(ALP). Under the catalytic action of horseradish peroxidase, hydrogen peroxide(H2O2) could generate hydro-xyl radicals(·OH), and ·OH oxidized o-dihydroxybenzene to produce o-benzoquinone subsequently, resul-ting in the fluorescence quenching of GQDs. ALP catalyzed the production of reductive ascorbic acid by ascorbic acid 2-phosphat. Ascorbic acid efficiently removed H2O2 and ·OH from the solution, leading to the inhibition of the production of o-benzoquinone and the fluorescence recovery of GQDs. Therefore, a highly sensitive determination strategy for ALP activity was established. Under the optimal experimental conditions, the detection limit of ALP activity was 0.084 U/L. This method was used to evaluate ALP activity in human serum samples. Such approach can provide theoretical basis for the diagnosis and treatment of ALP-related diseases.

    A Coumarin-based Ratiometric Fluorescent Probe for BF3 Detection in Solution and Air
    ZHAO Huijun, WU Tong, SUN Yue, DUAN Lian, MA Yanyu
    2021, 42(8):  2422-2427.  doi:10.7503/cjcu20210027
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    A selective and sensitive coumarin-based ratio fluorescent probe 3-p-methylbenzene-7-diethylamino coumarin(TDC) was developed for BF3 detection in dichloromethane and gas phase. The detection limit of BF3 was estimated to be 5.5×10-7 mol/L. The probe TDC showed a remarkable ratio fluorescence change in the presence of BF3 with a fast respond time. 19F NMR result demonstrated that the Lewis acid-base complexes formed between the diethylamino substituents in the probe and BF3 greatly influenced the intramolecular charge transfer(ICT) process. To meet the practical application, a simple test strip system was developed to detect BF3 in gas phase rapidly with obvious color changes.

    Colorimetry/Ratio Fluorimetry Determination of Glucose with Bifunctional Carbon Dots
    YUAN Chunling, YAO Xiaotiao, XU Yuanjin, QIN Xiu, SHI Rui, CHENG Shiqi, WANG Yilin
    2021, 42(8):  2428-2435.  doi:10.7503/cjcu20210019
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    Fe and N co-doped carbon dots(Fe,N-CDs) were prepared by hydrothermal method using biomass(leaf of syngonium podophyllum schott), ammonium ferric sulfate dodecahydrate and urea as raw materials, and their morphology and elemental composition were characterized by means of transmission electron micro-scopy(TEM) and X-ray photoelectron spectroscopy(XPS). The obtained Fe,N-CDs possessed both peroxidase-like activity and strong fluorescence emission at 450 nm. A dual signal(colorimetry and ratio fluorimetry)

    method<sup/>

    for the determination of H2O2was developed using Fe,N-CDs and o-phenylenediamine(OPD) as probe. When H2O2 was present, OPD was oxidized to 2,3-diaminophenazine(DAP) under the catalysis of Fe,N-CDs. DAP had a characteristic absorption peak at 420 nm. When excited at 360 nm, DAP had a strong fluorescence emission at 550 nm, quenching the fluorescence of Fe,N-CDs at 450 nm because of the inner filter effect. Results showed that the concentration of H2O2 could not only affect the color of the DAP but also the fluorescence intensity of DAP and Fe,N-CDs. Thus, the absorbance of DAP at 420 nm(A420) and fluorescence intensity ratio of DAP and Fe,N-CDs(I550/I450could be used for the quantitative analysis of H2O2. Considering that glucose oxidase can catalyze glucose oxidation to produce H2O2, a colorimetric and ratio fluorescence dual-signal method for glucose detection was further developed. Under the conditions of pH 5.4, temperature 40 ℃, 1.75 mmol/L OPD and reaction time 25 min, A420 and I550/I450 showed good linear relationship with the glucose concentration in the range of 1.0—100 μmol/L, and the detection limits(LOD) for glucose were 0.8(colorimetry) and 0.6(ratio fluorimetry) μmol/L, respectively. This dual-signal method was applied to the determination of glucose in human serum with satisfactory results.

    193 nm UV Photodissociation Mass Spectrometry for Ubiquitin Ions with Different Charge States
    ZHOU Min, SHI Yingying, LI Shuqi, ZHANG Kailin, CUI Yongliang, ZHANG Sen, ZHANG Xianyi, KONG Xianglei
    2021, 42(8):  2436-2442.  doi:10.7503/cjcu20210004
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    In recent years, the application of ultraviolet photodissociation(UVPD) in protein top-down mass spectrometry has attracted more and more attentions. In this study, the UVPD mass spectra of ubiquitin ions with different charge states were studied by combining a 193 nm laser with a fourier transform ion cyclotron resonance(FT-ICR) mass spectrometer. Results showed that the efficiency of ion fragmentation and trapping could be improved by introducing an appropriate amount of collision gas into the analysis cell during photolysis. Compared with the pure b, y ions produced in collision-activated dissociation(CAD) experiments, UVPD method produced more abundant fragment ions in both intensity and diversity. For +11 ubiquitin ions, the protein sequence coverage was close to 80%, which was much higher than the corresponding experimental results of CAD. However, different from the previous reports, the fragmentation coverage still showed a correlation with the charge state of the ions. For the lower charged protein ions, further research for a better dissociation efficiency and sequence coverage is still needed very much.

    Organic Chemistry
    Carbazole-derived Dicyanostilbene Two-photon Fluorescence Probe for Lipid Raft
    HUANG Chibao, KANG Shuai, PAN Qi, LYU Guoling
    2021, 42(8):  2443-2449.  doi:10.7503/cjcu20210140
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    Lipid raft is a microdomain which is rich in cholesterol and sphingolipid(sphingomyelin and glycosphingolipid) in the cytoplasmic membrane. They are involved in cellular processes such as cell transduction and protein transport, and are closely related to neurodegenerative diseases such as Alzheimer's disease and prion disease. Therefore, the studies on the dynamic physiological processes and the action mechanism of lipid raft are helpful to reveal its life mystery and its correlations with some diseases. The two-photon fluorescence probe for lipid raft became an indispensable sharp tool to achieve this goal. A carbazole-derived two-photon fluorescence probe for lipid raft(DLR) was developed and characterized. DLR belonged to push-pull electronic architecture(donor-bridge-receptor, D-π-A). The maximum emission wavelength of the probe increased with the medium polarity and its fluorescence intensity decreased with the polarity. The emission intensity of DLR in dipalmitoylphosphatidylcholine(DPPC) was 20 times higher than that in dioleoylphosphatidylcholine(DOPC), and the fluorescence intensity ratio of DLR in DPPC, Raft mix[n(DOPC)∶n(sphingomyelin)∶ n(cholesterol)=1∶1∶1] and DOPC was 20∶12.8∶1, and its fluorescence lifetime in DPPC was more than 2.2 times that in DOPC, which indicated that DLR could distinguish DPPC from DOPC. The two-photon action cross sections(Φδ) of DLR in DPPC and DOPC were 1350 and 67 GM, respectively. DLR was able to image lipid raft distribution in cells and tissues.

    Rhodium⁃catalyzed C—H Alkenylation of Indoles and Vinyltriethoxysilane
    LI Pengjie, ZHOU Chunni, WANG Zetian, ZHENG Ziang, ZHANG Yumin, WANG Liang, XIAO Biao
    2021, 42(8):  2450-2457.  doi:10.7503/cjcu20210107
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    A Rhodium-catalyzed direct C—H alkenylation of indoles using commercially available vinyltriethoxysilane as the vinylating reagent was developed. When the reaction was catalyzed by [RhCp*Cl22 with Cu(OAc)2 as oxidant in the presence of AgF in 1,2-dichloroethane at 90 ℃, a series of terminal vinylindole derivatives could be obtained in 42% to 88% yields. The kinetic isotopic effect experiment was conducted and a KH/KD value of 5.7 was obtained, which suggested that the C—H bond cleavage was involved in the rate- determining step. The competition experiment between differently substituted indoles indicated that electron-rich indoles were preferentially converted, suggesting that an electrophilic C—H activation process might be involved in this transformation. A possible reaction mechanism, including coordination, C—H bond activation, transmetallization, reductive elimination and oxidantion, was then proposed. Moreover, this synthetic method was successfully applied to the synthesis of δ-carboline derivative.

    Synthesis of Norephedrine in One Pot
    LUO Lei, MU Xiaoqing, WU Tao, NIE Yao, XU Yan
    2021, 42(8):  2458-2464.  doi:10.7503/cjcu20210078
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    In this study, a new biosynthetic pathway of norephedrine was constructed, through cascading the carboligation reaction catalyzed by acetohydroxyacid synthase Ⅰ(ASAHI) and reductive amination reaction ca-talysed by amine dehydrogenase(BbAmDH), the cheap substrate benzaldehyde, pyruvate and NH4Cl used as raw materials. Optimizing the reaction conditions of the two-step and one-pot method, the conversion rate of benzaldehyde was as high as 99% in the two-step and 83% in one-pot. Utilizing the strategy of feeding in one pot, the substrate and production inhibition effect of ASAHI was successfully relieved, and the benzaldehyde loading was increased to 100 mmol/L from 40 mmol/L in the batch reaction; the benzaldehyde conversion rate was increased to 90% from 83%, and the space-time conversion rate of benzaldehyde was increased by 2.7 times.

    Extraction, Structure Characterization and Biological Activities of Oligosaccharides from Auricularia heimuer
    HU Haocheng, LI Wenli, ZHANG Jianing, LIU Yubo
    2021, 42(8):  2465-2473.  doi:10.7503/cjcu20210064
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    In this study, Auricularia heimuer fermentation puree prepared by thermal explosion pretreatment was used as raw material. Crude Auricularia heimuer polysaccharide(CAHP) was extracted by hot water extraction. CAHP was degraded by a combination of H2O2 oxidative hydrolysis and ultrasonic physical hydrolysis. Then, CAHP was separated by anion exchange column chromatography and gel filtration column chromatography to obtain Auricularia heimuer oligosaccharide 1(AHO1). Analyzed by monosaccharide composition analysis, high-resolution mass spectrometry, infrared spectroscopy, and nuclear magnetic resonance, AHO1 is an oligosaccharide with a degree of polymerization of 2—10 connected by α-glycosidic bonds, which is composed of six kinds of monosaccharides, maliy mannose. The results of functional analysis showed that AHO1 had certain free radical scavenging ability and could effectively attenuate the oxidative stress response of HepG2 cells induced by H2O2. The results of antibacterial experiments showed that AHO1 not only has a good inhibitory effect on Escherichia coli DH5α and Staphylococcus aureus ATCC6538, but also can effectively inhibit the activity of genetically engineered bacteria with ampicillin resistance.

    Physical Chemistry
    Zr-MOF Hollow Nanospheres Supported Ionic Liquid for CO2 Cycloaddition Reaction
    LI Meiyan, CHEN Zijuan, WANG Shuhua, CHEN Chao
    2021, 42(8):  2474-2482.  doi:10.7503/cjcu20210221
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    Hollow nanosphere Void@UiO-66-Ⅰ and bulk UiO-66-Ⅰ were designed and prepared by post- synthetic modification(PSM) technique. Such two Zr-MOFs functionalized by quaternary ammonium salt possessed acid-base active sites and hydrogen bond donors. A series of characterization results demonstrated that the two catalysts were successfully synthesized and could be used to catalyze the cycloaddition reaction of CO2 and styrene oxide. Due to the quaternary ammonium salt of Void@UiO-66-Ⅰ with a large number of hydro-xyl groups and halogen anion, it could induce the epoxide ring-opening by hydrogen bond and nucleophilic attack of the iodide, promoting the reaction proceed smoothly. Moreover, the hollow structure of Void@UiO-66-Ⅰ was conducive to the mass transport. Therefore, it showed better catalytic performance than bulk UiO-66-Ⅰ catalyst for the reaction of CO2 and styrene oxide cycloaddition. Under optimal reaction conditions(120 ℃, initial CO2 pressure 1.2 MPa, 6 h), without solvent and co-catalyst, the yield and selectivity of styrene carbonate(SC) were 85.5% and 95.2%, respectively.

    Synthesis of Zn-Doped NiCoP Catalyst with Porous Double-layer Nanoarray Structure and Its Electrocatalytic Properties for Hydrogen Evolution
    WU Yaqiang, LIU Siming, JIN Shunjin, YAN Yongqing, WANG Zhao, CHEN Lihua, SU Baolian
    2021, 42(8):  2483-2492.  doi:10.7503/cjcu20210218
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    NiCoP is wildly accepted as one of the most potential catalysts for electrocatalytic hydrogen evolution reaction(HER) due to its high catalytic efficiency and low cost. However, the hydrogen bubble formation over catalyst surface during HER largely decreases the catalytic active sites and slows the mass transportation of electrolyte, resulting in a limited catalytic performance. In this paper, Zn-doped NiCoP catalyst with porous double-layer array structure on foam nickel was constructed by hydrothermal, followed with in?situ phospha?ting and HCl selective etching. Compared with the traditional single-layer array, the top nanoleaves array distributes uniformly on the bottom nanowires array, which maximizes the exposed catalytic active sites and provides a larger contact area for electrolyte. Moreover, the porous hierarchy also accelerates hydrogen bubble’s release. As a result, the optimized H-Zn-NiCo-P shows high electrocatalytic activity in alkaline electrolyte (1 mol/L KOH), with overpotentials of 59 and 156 mV at the current densities of 10 and 100 mA/cm2, respectively. The Tafel slope is 66 mV/dec and it shows excellent electrochemical stability. This research provides new ideas and solutions for the development of electrocatalysts with novel array structure.

    Construction of a Novel S-scheme CdS-BiVO4 Heterojunction Photoelectrodes and Research on Hydrogen Production
    XUE Jinbo, GAO Guoxiang, SHEN Qianqian, LIU Tianwu, LIU Xuguang, JIA Husheng
    2021, 42(8):  2493-2499.  doi:10.7503/cjcu20210212
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    The single component photocatalysts have low photocatalytic hydrogen production efficiency due to the serious recombination of photogenerated electrons and holes and the mismatch of redox capacity and light absorption range. CdS/BiVO4 and BiVO4/CdS S-scheme heterojunction film photoelectrodes were prepared via chemical bath deposition and successive ionic layer adsorption and reaction method, respectively. The morphology, structure, optical and photoelectrochemical properties of the two film electrodes were characte-rized by scanning electron microscopy(SEM), X-ray diffraction(XRD), ultraviolet-visible(UV-Vis) spectro-scopy, and electrochemical impedance spectroscopy(EIS), and the photocatalytic and photoelectrocatalytic hydrogen production properties of the two film electrodes were tested. The results show that S-scheme heterojunction formed between CdS and BiVO4, BiVO4/CdS shows the best photocatalytic hydrogen production performance, while CdS/BiVO4 shows the best photoelectrocatalytic hydrogen production performance. With the help of surface photovoltage technology, the formation process of the built-in electric field and the carrier transport mechanism of S-scheme heterojunction in the two film electrodes are explored.

    A Highly Efficient One-step Preparation Method of Nano-silicon and Carbon Composite for High-performance Lithium Ion Batteries
    WU Zhuoyan, LI Zhi, ZHAO Xudong, WANG Qian, CHEN Shunpeng, CHANG Xinghua, LIU Zhiliang
    2021, 42(8):  2500-2508.  doi:10.7503/cjcu20210165
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    Lithium-ion batteries(LIBs) have been widely applied in portable electronic devices and electric vehicles and energy storage industries. However, with the rapid development of our society, it is more and more difficult to meet the increasing demand of people for commercial LIBs because their energy densities are generally lower than 250 W·h/kg. Thus, it is urgent to further develop higher-capacity electrode materials to efficiently increase the energy densities of LIBs. Silicon is a very attractive anode material for LIBs with superhigh theoretical capacity(4200 mA·h/g), suitable working potential and abundant earth reserve. Although the pure Si material suffers from poor cycling performance due to very large volume change during repeated lithiation/delithiation, recent researches have shown that the homogeneous carbon composite for nano-silicon could improve the cycling performance effectively. But the preparation methods of nano-silicon and carbon composite are still very complicated, limiting the large-scale preparation and application. A highly efficient one-step method to synthesize the homogeneous composite between nano-silicon and carbon sheet(nano-Si/C) was developed through mechanically milling SiCl4, Mg2Si and commercial carbon sheets. During the milling process, nano-Si is produced from the bottom-up reduction of SiCl4. The in situ formed nano-Si can directly grow on the carbon sheet, further leading to homogeneous composite between nano-Si and carbon sheet. This method possesses a very high reaction efficiency as reactants convert into nano-Si and MgCl2 completely without the gene-ration of any impurities. The scanning electron microscopy(SEM) and transmission electron microscopy(TEM) display that the nano-Si supported on carbon sheet is around 30—80 nm in diameter. As the anode material for LIBs, the nano-Si/C sample shows a very high reversible capacity(2450 mA·h/g at 0.2 A/g), good rate performance(1040 mA·h/g at 4.8 A/g) and excellent long cycling stability(retaining 1400 mA·h/g even after 600 cycles at 2 A/g). The cyclic voltammograms of nano-Si/C at different sweep rates demonstrate the electrochemical kinetics is controlled by both lithium diffusion process and pseudocapacitance effect. The outstan-ding electrochemical performance is mainly attributed to the uniform composite nanostructures between small-sized nano-Si and carbon sheet, which can maintain the structural integrity and stable electrochemical properties after lithiation/delithiation cycles, as suggested by the electrochemical impedance spectroscopy and SEM images tested after cycles. Combining cheap reactants, simple preparation step and homogeneous composite structure, this method is very promising for low-cost and large-scale preparation of high-performance Si and carbon composite anode with good application prospect.

    Preparation and Photoelectrochemical Performance of Bi1-xFexVO4 Thin Film Photoanodes
    TANG Ding, ZHONG Shuiping
    2021, 42(8):  2509-2517.  doi:10.7503/cjcu20210162
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    Herein, Bi1-xFexVO4x=0, 0.05, 0.10, 0.25, 0.40) thin films were prepared on fluorine-doped tin dioxide(FTO) conductive glasses by one-step drop-coating approach, and their structural, morphological, optical and photoelectrochemical(PEC) properties were characterized. It is found that Bi1-xFexVO4 thin films with Fe addition show the better PEC performance compared with BiVO4 thin film. At the potential of 1.23 V(vs. RHE), a highest photocurrent density of 0.50 mA/cm2 for water oxidation is obtained for 25% Fe-BiVO4(the actual Fe content is 22.5%) thin film in 0.1 mol/L potassium phosphate buffer solution(pH=7.0), which is three times higher than that of BiVO4 thin film. Combined with X-ray diffraction(XRD), Raman spectroscopy and X-ray photoelectron spectroscopy(XPS) analyses, it is confirmed that Fe3+ presents in form of FeVO4 in the Bi1-xFexVO4 thin films, thus actually a BiVO4/FeVO4 composite film is prepared. The UV-Vis measurements reveal that all the Bi1-xFexVO4 thin films exhibit an optical band gap of 2.4—2.5 eV. After eliminating the effort of iron-based OER catalysts, the improved PEC activity of 25% Fe-BiVO4 thin film could be attributed to the increment of charge transfer efficiency(ηtrans) and separation efficiency(ηsep), which is also verified by electrochemical impedance spectroscopy(EIS) tests. The flat band potentials of BiVO4 and FeVO4 thin films are determined to be 0.10 V and 0.42 V(vs. RHE) from Mott-Schottky measurements. Based on the measured optical band gap and flat band potential, a schematic diagram of band structure is plotted, and the result displays that a type Ⅱ band alignment is formed between BiVO4 and FeVO4, which could promote the separation and transfer of photogenerated electron-hole pairs. Therefore, the mechanism for the improved PEC performance of 25% Fe-BiVO4 thin film could be explained by favorable separation and transfer of carriers resulted from the type Ⅱ band alignment.

    Theoretical Study of the Catalytic Activity of VmoLac Non-specific Substrates Based on Molecular Dynamics Simulations
    LI Congcong, LIU Minghao, HAN Jiarui, ZHU Jingxuan, HAN Weiwei, LI Wannan
    2021, 42(8):  2518-2528.  doi:10.7503/cjcu20210136
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    The molecular dynamics simulation method was used to study the catalytic activity of VmoLac non-specific substrates. Four systems of VmoLac/3-oxo-C10-AHL, VmoLac/3-oxo-C6-AHL, VmoLac/γ-nonalacton and VmoLac/ethyl-paraoxon complexs were simulated. The main reasons for the conformational changes caused by the binding of different substrates to VmoLac were analyzed. The analysis results show that the 3-oxo-C10-AHL and γ-nonalacton combination can make the active pocket near Loop8 structure domain motion obviously. The flexible conformation made it easier for the substrate to bind to the outside of the hydrophobic channel of Loop8, which was conducive to the catalytic reaction. VmoLac activity around the pocket gating residues W264 and Y230 changes will affect the distance between the combination of the substrate. The distance between Y98 and the carbonyl carbon of long-chain lactone and nonolactone was relatively small, while the distance between Y98 and the carbonyl carbon of short-chain lactone and the phosphorus atom of phosphorus oxide was relatively large. Shorter distance was more conducive to the occurrence of nucleophilic offensive reaction. D257 was the key residue that initiated the VmoLac catalytic reaction. When VmoLac catalyzed 3-oxo-C10-AHL or γ-nonalacton, D257 formed more hydrogen bonds with polarized water and substrate, which made the substrate more easily bind to the enzyme. VmoLac had a stronger ability to catalyze long-chain lactones than short-chain lactones, and a stronger ability to catalyze long-chain lactones than phosphorus oxides from the perspective of theoretical catalytic mechanism, which provides theoretical proof for the experimental structure.

    Hierarchical Mesoporous-microporous TS-1 Single Crystal Catalysts for Epoxidation of Allyl Chloride
    ZHANG Xu, QUE Jiaqian, HOU Yuexin, LYU Jiamin, LIU Zhan, LEI Kunhao, YU Shen, LI Xiaoyun, CHEN Lihua, SU Baolian
    2021, 42(8):  2529-2539.  doi:10.7503/cjcu20210134
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    Epoxidation catalytic technology is important for preparing organic chemical raw materials and fine chemical products. But it has drawbacks such as low catalytic efficiency and serious pollution problem. The key to realize sustainable energy development is to develop green epoxidation catalytic techniques. Selective oxidation over titanosilicate zeolite TS-1 is the key to achieve green epoxidation process. Aiming at solving the intracrystalline diffusion limitations in microporous zeolites caused by their relatively small micropores, this paper focuses on design and synthesis of hierarchically mesoporous zeolite TS-1 single crystals, investigation and development of the synthesis methods, and the influence of hierarchically meso-microporous hierarchy on the catalytic epoxidation of allyl chloride performances. Compared with microporous zeolite TS-1, the hierarchically mesoporous zeolite TS-1 has better catalytic activity.

    First-principles Study on the Catalytic Effect of Co,P co-Doped MoS2 in Lithium-sulfur Batteries
    CHEN Mingsu, ZHANG Huiru, ZHANG Qi, LIU Jiaqin, WU Yucheng
    2021, 42(8):  2540-2549.  doi:10.7503/cjcu20210110
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    In lithium-sulfur batteries, metal compound catalytic materials enhance the electrochemical redox reaction kinetics, fundamentally prevent the shuttle effect of polysulfides, and improve the electrochemical performance. MoS2 material has received widespread attention due to the affinity for polysulfides and catalytic ability. However, the base surface that occupies most of the reaction interface exhibits weaker catalytic activity than the few edge sites. The Co, P co-doping strategy was used for the first time to modify MoS2 material as cathode material in lithium-sulfur battery. Compared with undoped and Co single-doped materials, it achieves excellent discharge capacity, rate performance and cycling stability. To explore the origin of Co, P co-doping MoS2 to improve the electrochemical performance of lithium-sulfur batteries, the first-principles research was carried out, clarifying the adsorption and conversion of polysulfides on the surface of undoped, Co single-doped, Co, P co-doped MoS2. The calculation results indicate that the adsorption energy shows the trend of undoped <Co single doped <Co, P co-doped MoS2. The Li—S and S—P double bonding between the co-doped surface and polysulfides make Co, P co-doped MoS2 have the greatest adsorption capacity. Additionally, the significant stabilizing effect for discharge product Li2S reduces the energy requirement of the dissociation step and increases the overall energy release during the conversion process, providing driving forces for the polysulfide conversion. These two factors jointly enhance the catalytic activity of MoS2, effectively inhibit the shuttle effect, and improve the electrochemical performance of the battery. It is hoped that the conclusion could promote the application of surface modified metal sulfide catalytic materials in lithium-sulfur batteries.

    Prediction of the Binding Site of PIP2 in the TREK-1 Channel Based on Molecular Modeling
    LEI Xiaotong, JIN Yiqing, MENG Xuanyu
    2021, 42(8):  2550-2557.  doi:10.7503/cjcu20210106
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    Phosphatidylinositol 4,5-bisphosphate(PIP2) is a type of signaling phospholipid molecule distri-buted in the inner layer of the plasma membrane, which has regulatory effects on various transmembrane proteins such as potassium, sodium, chloride ion channels and transporters. TREK-1 is an important background potassium channel, which is regulated by various factors such as temperature, mechanical stretch, intracellular pH, etc. PIP2 activates the TREK-1 channel in a specific concentration range. Treatment of poly-lysine to inhibit the PIP2 in the inside-out patch clamp can cause the TREK-1 channel to close. Molecular docking and all-atom molecular dynamics simulation were used to explore the interaction of PIP2 on the two-pore-domain potassium channel TREK-1. Molecular docking calculations showed that PIP2 has two possible binding sites on the TREK-1 channel to activate the channel. Further use of molecular dynamics simulations and potential of mean force(PMF) calculations showed that the site located between the helix M4 and helix M1 is the preferential binding site for PIP2 to activate TREK-1. The simulation displayed the possible configuration of PIP2 bin-ding to TREK-1. The phosphate groups in inositol head of PIP2 form stable salt bridges with the basic residues K45 located on M1, and K304 and R311 located on M4; K304 and R311 have been verified by mutation experiments, which play an important role in the activation of TREK-1 by PIP2. In addition, a series of hydrophobic residues on the helix M1 play key roles in stabilizing the long fat chains of PIP2.

    Pyroelectrically-induced Catalytic Performance of Zr-based MOF Under Cold-hot Alternation
    CHANG Shuqing, XIN Xu, HUANG Yaqi, ZHANG Xincong, FU Yanghe, ZHU Weidong, ZHANG Fumin, LI Xiaona
    2021, 42(8):  2558-2563.  doi:10.7503/cjcu20210083
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    Pyroelectrically-induced catalysis is emerging as a green and highly efficient technology for the degradation of dye wastewater. Zirconium metal organic framework [NH2-UiO-66(Zr)], as the pyroelectric material, was firstly applied in the degradation of Rhodamine B through harvesting cold-hot alternation energy. NH2-UiO-66(Zr) showed excellent ferroelectric response, in which the positive and negative electric charges could be generated on the surface via the pyroelectric effect under cold-hot alternation. The pyroelectrically induced charges would combine with the hydroxide and the dissolved oxygen to form hydroxy radicals and superoxide radical, resulting in the decomposition of dye. The degradation efficiency of RhB can be up to 99.5% over NH2-UiO-66(Zr) after 100 cold-hot cycles, exhibiting good reusability. This work can broaden the application of MOFs and also provide a new avenue for the treatment of dye wastewater.

    Preparation Mechanism and Application of Alcohol⁃modified Fe3O4 Magnetic Nanoparticles
    XU Yan, YANG Hongguo, NIU Huibin, TIAN Hailin, PIAO Hongguang, HUANG Yingping, FANG Yanfen
    2021, 42(8):  2564-2573.  doi:10.7503/cjcu20210077
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    Herein, modified Fe3O4 particles(named as E-Fe3O4, P-Fe3O4 and D-Fe3O4, respectively) were prepared by chemical precipitation method using ethyleneglycol(EG), polyethylene glycol(PEG) and mannitoll(D-M) as the separated modifier. The results showed that the alcohol molecules can be successfully modified on the surface of Fe3O4 particles, and the morphology, size, crystal phase and magnetic properties of Fe3O4 particles are not significantly affected. Modification mechanisms of Fe3O4 samples are studied by Fourier transform infrared spectroscopy, ion selective electrode method, Zeta potential and water contact angle tests. It is shown that the modification mechanism of P-Fe3O4 and D-Fe3O4 samples are associated with the hydrogen bonding of water molecules mediated, while more stable hydrogen bond can be formed between ethylene glycol and hydroxyl group on the surface of E-Fe3O4. Consequently, ethylene glycol was still fixed on the surface of Fe3O4 even under high temperature treatment(120 ℃). E-Fe3O4 with hydrophobic group on the surface exhibits optimal hydrophilicity(contact angle was 32.92°) and water dispersion behavior(diameter was about 200―300 nm). E-Fe3O4 with negative surface charge can be applied to remove cationic dye crystal violet(CV) from water and adsorption capacity was 19.33 mg/g, which was 2.3 times of that pristine Fe3O4(8.41 mg/g). Besides, the addition of isopropanol is beneficial for CV desorption. This study not only provides a new method for preparing magnetic nano-Fe3O4 adsorption material, but also provides a theoretical basis for its application in the separation and adsorption of dye wastewater.

    Size Polydispersity of Oleic Acid Vesicles and Effects of Diols on the pH Window of the Vesicles
    FAN Ye, FAN Mengqi, FANG Yun, LI Lei, PAN Hongyang, XIA Yongmei
    2021, 42(8):  2574-2580.  doi:10.7503/cjcu20210053
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    Oleic acid(OA) was selected as a model fatty acid, and the pH window of OA vesicles was 8.2—10.1 confirmed by phase division in the pH titration curve depending on the observation of laser Tyndall effects. Particle sizes and morphology of the OA vesicles were characterized by optical microscopy, confocal laser microscopy and freeze-fracture transmission electron microscopy. It is found that the micro- and sub- micro-sized fatty acid vesicle(FAV) are multilamellar vesicles while nano-sized FAV are unilamellar vesicles, which coexist in the aqueous solution, indicating the size polydispersity of OA vesicles. A series of short-chain diols are used to assist the formation of OA vesicles, which showed that the short-chain diols are favorable for the pH window extension of FAV. The extension direction may depend on the modes of either surface hydrogen bonding or hydrophobic insertion. It is suggested that if more hydroxyl groups of the used diol remained on the FAV surface after interaction, the acidic pH window would extend.

    Activation of Peroxymonosulfate by Single Atom Catalysts Ni⁃N⁃C for High Efficiency Degradation of Phenol
    PENG Xiaoming, WU Jianqun, DAI Hongling, YANG Zhanhong, XU Li, XU Gaoping, HU Fengping
    2021, 42(8):  2581-2591.  doi:10.7503/cjcu20210009
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    A single atom catalyst(Ni-N-C-10) supported on lignin biochar was prepared via calcination method, which was used to activate peroxymonosulfate(PMS) to degrade phenol. The prepared catalysts were characterized by means of scanning electron microscopy(SEM), transmission electron microscopy(TEM), X-ray powder diffraction(XRD), N2 adsorption-desorption analysis and X-ray photoelectron spectroscopy(XPS). It was proved that the atom dispersed catalyst Ni-N-C-10 was synthesized. The effects of dicyandiamide dosage in the preparation process, catalyst dosage, PMS dosage, pH value and temperature on phenol degradation were also studied. The results showed that the addition of dicyandiamide 10 times the weight of lignin was more conducive to the atom dispersion. Besides, Ni-N-C-10/PMS system could effectively activate PMS and degrade phenol at lower catalyst and PMS dosage in a wide range of pH(3―9). In addition to efficient degradation of phenol, it could also rapidly degrade a variety of organic pollutants such as p-chlorophenol, bisphenol A, tetracycline and methylene blue. EPR detection and radical quenching experiments showed that 1O2 acted as the dominant active specie in the Ni-N-C-10/PMS system for phenol degradation. The XPS analysis of Ni-N-C-10 catalyst before and after the reaction showed that the catalytic degradation efficiency of the catalyst was positively correlated with Ni site. This work proves that the Ni-N-C-10/PMS system could efficiently degrade the phenol in water and has potential applications.

    Design and Construction of N-Doping Carbon in⁃situ Coated Cu2O/Co3O4@C Heterostructured Composite Material for Highly Efficient Lithium-ion Storage
    TIAN Runsai, LU Qian, ZHANG Hongbin, ZHANG Bo, FENG Yuanyuan, WEI Jinxiang, FENG Jijun
    2021, 42(8):  2592-2601.  doi:10.7503/cjcu20210088
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    Transition metal oxides have been intensively studied as potential anode materials for the next generation lithium-ion batteries due to their high theoretical capacity, low cost and higher safety. Herein, the nano-cubic Cu2O was fabricated through simple liquid-phase method followed by the self assembly of ZIF-67/ZIF-8 bi-metal organic framework(MOF), then the hierarchical porous Cu2O/Co3O4@C heterostructured composite material with Co3O4 and N-doped carbon as double shell was successfully constructed. XRD, SEM, TGA, BET, Raman spectra and XPS characterization proved the successful engineering of the heterostructured Cu2O/Co3O4@C composite material. Benefiting from the double-shell and hierarchical porous construction, the volume expansion of the composite material during cycling was effectively restrained. The SEM images after even 100 cycles proved the maintaining of the original morphology and structure of the composite material. The sufficient electrolyte infiltration owing to the porous surface structure, the built-in electric field at the heterostructure interface and the coating of defective N-doped carbon mutually enhance the electronic and ionic conductivity and facilitate the reaction kinetics. The synergistic effects of heterostructure design, morphology regulation, porous properties and N-doped carbons coating endow the Cu2O/Co3O4@C composite material with excellent electrochemical performance. An as high initial discharge capacity as 2065 mA·h/g at 0.1 A/g and reversible discharge capacity of 360 mA·h/g at 2 A/g are delivered, and the stable discharge capacity of 550 mA·h/g maintains after 350 cycles at 1 A/g.

    Polymer Chemistry
    Evolution of the Radicals in γ-Rays Irradiated Medical Grade Ultra-high Molecular Weight Polyethylene
    LIU Simei, LIU Weihua, LU Manli, ZHANG Wenli, SHEN Rongfang, WANG Mouhua
    2021, 42(8):  2602-2608.  doi:10.7503/cjcu20210201
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    Medical grade ultra-high molecular weight polyethylene(UHMWPE) was irradiated with γ-rays. The types of irradiation-induced free radicals and their decay behavior under argon and different partial pressures of oxygen were studied by electron spin resonance spectroscopy(ESR). In argon, the alkyl radicals and allyl radicals are the main radical species with a total radiation chemical yield of 0.48/100 eV. Alkyl radicals have poor stability with a life time about 1 d at room temperature. In oxygen-containing atmosphere, free radicals are decayed mainly by oxidation reaction and the decay rate increases with the increase of oxygen partial pressure. The half-life of free radicals decreases from 224.0 h in 1×105 Pa argon to 1.8 h in 5×105 Pa O2. It is estimated that the migration rate of free radicals trapped in the crystal region to the surface of the microcrystalline is very fast at room temperature, on the order of hours.

    Protein-based Hydrogel Assisted by Hofmeister Effect for Strain Sensor
    CAI Yaqian, ZHANG Jiahuai, LIU Fangzhe, LI Haichao, SHI Jianping, GUAN Shuang
    2021, 42(8):  2609-2616.  doi:10.7503/cjcu20210191
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    Natural protein-based hydrogels have been widely studied in recent years because of their good biocompatibility. However, the preparation of natural protein-based hydrogels with excellent toughness and electrical conductivity remains a challenging problem. Using sodium caseinate and gelatin as raw materials, a kind of natural protein-based hydrogel was prepared through Hofmeister effect by soaking in ammonium sulfate solution. The soaking method overcomed the weakness of soft and fragile protein-based hydrogel. The test results showed that the hydrogel had excellent mechanical properties. The maximum tensile stress of hydrogel was 3.55 MPa, and the maximum tensile strain was 1375 %. The maximum conductivity of the hydrogel was 0.0954 S/cm, and the conductivity sensitivity factor was 0.53. The hydrogel sensor had distinguishing ability for different strains, and can monitor the movement of different parts of human body. The hyderogel sensor showed accuracy and stability in the signal transmission process, which makes the hydrogel an ideal material for monitoring human health and movement. In addition, the hydrogel showed good shape-memory performance. This strategy opens up a new field of vision for the preparation of strong conductive hydrogels, and expands the application prospect of hydrogels in biomedical and electronic sensing fields.

    Predicting the Glass Transition Temperature of Polyimides: Group Additive Property Method and Assigning the Group Contributions to Unknown Groups
    HUANG Congcong, ZHANG Baoqing, LIU Chenyang
    2021, 42(8):  2617-2626.  doi:10.7503/cjcu20210178
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    Group additive property(GAP) method considers that the property of polymer can be calculated from the contribution of the groups that make up the main and side chains of the repeating unit. The glass transition temperature(Tg) and melting point et al. for polymer can be calculated by GAP. Aromatic polyimides are high-performance polymers obtained by dehydration condensation between dianhydride and diamine. Quantitatively predicting the glass transition temperature of polyimide from the chemical structure is helpful to optimize and prescreen the monomer molecular structure, but it remains a challenge. The Tg values of 74 polyimides were calculated by known group contributions offered by van Krevelen, the predicted Tg values are in good agreement with the experimental ones, with the standard deviation(s) of 21 K and R2 of 0.88, but there is still a large systematic error due to the deviation of the fitted curve slope(0.78) from 1. Therefore, the Tg values of these 74 polyimides were recalculated after the contribution values of the groups contained in these polyimides were corrected. The results showed a good correlation(R2=0.88, s=18 K) with experimental values, and the slope of the fitted curve(0.94) was close to 1, which means the systematic error is effectively eliminated. The corrected group contribution values were used in following calculations. A method to assign the group contribution values to unknown groups was proposed. Then the Yg values of 7 unknown dianhydrides and 6 unknown groups contained in dianhydrides or diamines were calculated by using this assignment method. The reliability of the contribution values of the 13 groups was verified by using the data of a training set(82 polyimides) and a test set(35 polyimides). This correction method and the assignment method presented in this work can also be used to other heteroaromatic polymers.

    Preparation of MWCNTs/PEEK Electromagnetic Shielding Composites with Sandwich Structure
    WU Tonghua, YUE Xigui, MEI Xiaohan, LIANG Liubo, PENG Xin, MA Youmei, ZHANG Shuling
    2021, 42(8):  2627-2634.  doi:10.7503/cjcu20210161
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    The multi-walled carbon nanotubes/polyether ether ketone electromagnetic shielding composites with sandwich-structure were prepared by using polyether sulfone(PES) as binder, multi-walled carbon nanotubes(MWCNTs) as core-layer, and polyether ether ketone(PEEK) film as surface-layer. As a result, the average thickness of PEEK/3(1PES∶4MWCNTs)/PEEK composite was only 0.28 mm when an appropriate amount of binder PES was introduced into the core-layer and the number of core-layers was increased to three. And its density, tensile strength, 5% mass loss temperature(Td,5%), conductivity, electromagnetic shielding value and specific electromagnetic shielding value can reach 1.349 g/cm3, 80 MPa, 581.8 ℃, 2.6 S/cm, 32 dB and 115 dB/mm, respectively, indicating that the composite has light weight, thin thickness, good mechanical properties and high electromagnetic shielding performance. These excellent comprehensive performances can be attributed to the introduction of appropriate amount of PES into the MWCNTs core-layer as binder during the preparation of composite with sandwich-structure, which can enhance the interface between the carbon nanotubes in the core-layer and between the core-layer and the surface-layer, followed by the improvement in the mechanical properties of the composite. At the same time, the dense conductive network formed by the carbon nanotubes in the core-layer can endow the composite with high electromagnetic shielding performance.

    Synthesis and Properties of Sulfonated Poly(phthalazinone ether phosphine oxide)s with Perfluorobiphenyl Moieties for Proton Exchange Membranes
    FU Zhinan, TAN Yunlong, XIAO Guyu, YAN Deyue
    2021, 42(8):  2635-2642.  doi:10.7503/cjcu20210095
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    The poly(phthalazinone ether phosphine oxide)s with perfluorobiphenyl moieties were synthesized by copolycondensation of decafluorobiphenyl, bis(4-fluorophenyl) phenylphosphorus oxide, and 4-(4-hydrolphenyl) phthalazinone, which were then converted to the sulfonated poly(phthalazinone ether phosphine oxide)s with perfluorobiphenyl moieties(sPEPOF-xx means the molar percentage of F-containing units) by sulfonation. The highly hydrophobic perfluorobiphenyl moieties facilitate to form the microphase seperation structures within polymer membranes, increasing the proton conductivity and decreasing the swelling ratio, thus the resultant membranes display superior comprehensive properties. At 80 ℃, the sPEPOF-25 membrane presents a swelling ratio of only 10%, about half that of Nafion 117 membrane, whereas its proton conductivity is 0.099 S/cm, which is 1.2 times that of Nafion 117 membrane. It also possesses excellent thermal stability and oxidation resistance, showing potential application prospect.

    Fabrication of Poly(p-xylene) Nanofiber Arrays by CVD Liquid Crystal Template Method and Their Degradability
    XIE Fan, CHEN Shanshan, ZHUO Longhai, LU Zhaoqing, GAO Kun, DAI Qiyang
    2021, 42(8):  2643-2650.  doi:10.7503/cjcu20210074
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    Benefiting from the superior biocompatibility and chemical stability of poly(p-xylylene)(PPX), it is of great significance to construct biodegradable PPX nanofiber arrays mimicking extracellular matrix structure in the bioengineering field. To tackle the problems of fabrication and degradation for PPX nanofiber, BMDO/PPX-CH2OH copolymer nanofiber arrays were prepared via chemical vapor deposition(CVD) using liquid crystal as template, 4-hydroxymethyl-p-xylene(PCP-CH2OH) as precursor of poly(4-hydroxymethyl-p-xylene)(PPX-CH2OH) and 5,6-benzo-2-methylene-1,3-dioxyheterocyclic heptane(BMDO) was introduced to copolymerize with PCP-CH2OH to endow the molecular chains with degradable property. The results indicated that PCP-CH2OH was successfully copolymerized with BMDO via CVD approach, and the copolymer nanofiber arrays were obtained. The morphology of the copolymer nanofiber arrays was related to the sample holder temperature and deposition rate, while the mass ratios of BMDO to PCP-CH2OH showed no obvious effect. The optimized CVD process is that the sample holder temperature is about -10 ℃, the deposition rate is about 0.01 nm/s, and the mass ratio of BMDO to PCP-CH2OH is 10∶1. The as-prepared copolymer nanofiber arrays could be degraded effectively in the carbonate buffer solution(0.1 mol/L Na2CO3+0.1 mol/L NaHCO3) at 37 ℃. The ester group in the nanofiber arrays could be decomposed completely after 23 d, and the nanofiber arrays became tiny fragments after 30 d, indicating that the nanofiber arrays were basically completely degraded.

    Preparation and Performance Analysis of Extremely High Strength Self-repairing Waterborne Polyurethane Adhesive Based on Oxime-carbamate
    LI Cong, LIU Huanhuan, YANG Guihua, TIAN Zhongjian, YAN Jiaqiang, JI Xingxiang, HAN Wenjia, CHEN Jiachuan
    2021, 42(8):  2651-2660.  doi:10.7503/cjcu20200824
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    From the perspective of recycling, commercial polyurethane hot-melt adhesives (HMA) could be reused many times via hot melting. However, the performance degradation after recylcing seriously impaired the reuse value. Although thermosetting structures could improve the performance, the material would not be reused once it was cured in view of the above challenges. A new water-based emulsion with high strength and dynamic network structure was synthesized from dimethylglyoxime, which was based on the thermal reversible bonding of carbamate ester, a commercially available chemical as the building block. In this paper, the rever-sible bonding characteristics of oxime-carbamate were analyzed by variable temperature infrared spectroscopy and differential scanning calorimetry. The dynamic dissociation phenomenon of the network at high temperature was strongly verified. The corresponding network relaxation behavior was quantitatively studied by dynamic mechanical spectrometer. The results showed that the proper hard segment content and structural design would give the adhesive the extremely high bonding strength (25 MPa, the commercially available hot-melt adhesive <6 MPa), excellent emulsion stability (particle size <100 nm), and the repair efficiency closed to 97% (lap shear test at 160 ℃ for 10 min). These waterborne emulsions had the characteristics of high strength, self repair and expandability, which opened up a feasible way for commercial application of this functional material in the field of adhesives.

    Materials Chemistry
    Preparation and Photoelectric Properties of Germanium Sulphoselenide Photodetector
    LIANG Xuejing, ZHAO Fulai, WANG Yu, ZHANG Yichao, WANG Yaling, FENG Yiyu, FENG Wei
    2021, 42(8):  2661-2667.  doi:10.7503/cjcu20210154
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    Germanium monochalcogenides are important members of group Ⅳ—Ⅵ semiconductor materials, with abundant reserves, low cost and low toxicity. Due to suitable band gap, high carrier mobility and light absorption coefficient, they have become the ideal choices for sustainable optoelectronic devices. Alloy enginee-ring is an important method for band gap tunning, which can adjust the light absorption range and even suppress the recombination of carriers, thereby improving the performance of photodetectors. In this work, a ternary alloy of germanium sulphoselenide(GeS0.5Se0.5) was synthesized by high-temperature solid-state reaction, and then the nanosheet with a lateral size of ca. 12 μm was prepared by micromechanical exfoliation. With the chromium(10 nm)/gold(120 nm) electrode as the contact electrode, a GeS0.5Se0.5 photodetector was prepared for the first time, and its photoelectric properties were explored. The results show that the nanosheet has good crystalline quality, sulfur and selenium atoms are uniformly distributed, and the optical band gap is 1.3 eV between GeSe(1.1—1.2 eV) and GeS(1.55—1.65 eV). Under 515 nm light excitation, the photodetector exhi-bits a very efficient, fast and stable optoelectronic properties, with a ultra-high specific detectivity(D*) of 4.52×1013 Jones, a high photoresponsivity(Rλ) of 1.15×104 A/W, and an external quantum efficiency(EQE) of 2.79×106%. In short, this research has contributed a very promising new type of ternary semiconductor with a narrow band gap to the field of optoelectronic devices, and provided a certain reference and guidance for the research of high-performance optoelectronic devices.

    Synthesis, Aggregation-induced Emission and Piezofluorochromic Properties of 9,10-Bis(N-phenylindole-3-vinyl)anthracene
    LIU Wei, YAO Wei, ZHOU Mingming, YOU Qi, NIE Yong, JIANG Xuchuan
    2021, 42(8):  2668-2672.  doi:10.7503/cjcu20210071
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    A fluorescent compound 9,10-bis(N-phenylindole-3-vinyl) anthracene(IA-Ph) was obtained by a simple Wittig reaction. The structure of IA-Ph was confirmed by nuclear magnetic resonance and mass spectrometry. The photophysical properties of IA-Ph were characterized by fluorescence emission spectrum and ultraviolet absorption spectrum. It was found that IA-Ph has both aggregation-induced fluorescence(AIE) and piezofluorochromic(PFC) properties. Compared with the fluorescence intensity in pure tetrahydrofuran(THF) solution, the fluorescence intensity of IA-Ph in the mixed solution with V(THF)∶V(H2O)=1∶9 was increased by 12 times, showing an obvious AIE effect. By simple mechanical grinding, the compound could be transformed from initial green light to an orange-red light with a spectral red shift of 68 nm. Under various external stimuli, the compound IA-Ph could change reversibly between green and orange-red fluorescence.

    Effect of Aromatic Substituent on Chiral Recognition of Helical Polyacetylene-based Chiral Stationary Phases for High-Performance Liquid Chromatography
    SHI Ge, XU Qian, DAI Xiao, ZHANG Jie, SHEN Jun, WAN Xinhua
    2021, 42(8):  2673-2682.  doi:10.7503/cjcu20210062
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    Three proline-derived acetylene monomers,(S)-2-ethynyl-N-aromatic carbamoyl pyrrolidine, were synthesized and polymerized under the catalysis of (bicyclo[2.2.1]hepta-2,5-diene)chlororhodium(I) dimer and triethyeamine{[Rh(nbd)Cl]2-Et3N}. The chiral recognition ability of the resultant optically active helical polymers as chiral stationary phases(CSPs) toward nine substitutes was evaluated by high-performance liquid chromatography. These polymers displayed satisfactory enantioseparation ability for three hydrogen-bond(HB) donating molecules, benzoin(α=1.35—1.44), 2,2,2-trifluoro-1-(9′-anthryl)ethanol(α=1.11—1.53), and 1,1′-bi(2-naphthol)(α=1.09—1.11), as well as cobalt(Ⅲ) acetylacetonate(α=1.84—2.38) when the mixture of hexane and isopropanol(volume ratio 9∶1) was used as the eluent. Whereas, when pure hexane was employed as the eluent, 2,2-dimethyl-1-phenyl-1-propanol(α=1.12—1.22) was stereoselectively discriminated by three polymers and 2-phenylcyclohexanone(α=1.11) by poly[(S)-2-ethynyl-N-(2′-naphthyl carbamoyl) pyrrolidine]. Based on NMR, Raman spectra, polarimetry, UV-Vis absorption and circular dichroism spectra, along with liquid chromatography, the correlations between aromatic structure and linking position with polymeric helical conformation as well as optical resolving power were investigated. Molecular docking results suggested that the 1-naphthyl group exhibited larger steric effect over 2-naphthyl group, and facilitated the formation of stronger intramolecular HBs, which impeded chiral discrimination toward giant racemates(such as 1,1′-binaphthyl-2,2′-diol). Compared to phenyl, naphthyl favored the enantioselective π-π interactions between polymers and enantiomers, enhancing the selectivity of steric fit and chiral resolving power of CSPs.

    Trehalose-modified Poly(vinyl alcohol) and Their Antifogging/Antifrosting Coatings
    BAI Jingqi, BAI Shan, REN Lixia, ZHU Kongying, ZHAO Yunhui, LI Xiaohui, YUAN Xiaoyan
    2021, 42(8):  2683-2688.  doi:10.7503/cjcu20210060
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    Trehalose-grafted poly(vinyl alcohol)(PVA-g-Tre) was synthesized from carboxylated trehalose and poly(vinyl alcohol)(PVA), and the hydrophilic semi-interpenetrating polymer network antifogging/ antifrosting coatings were further prepared from the trehalose-modified polymer with ethylene glycol dimethacrylate via photoinitiated polymerization. The chemical structure of PVA-g-Tre was characterized by proton nuclear magnetic resonance and Fourier transform infrared spectroscopy. The roughness and wettability of the coating surface as well as hydrogen bonding between water and the polymer were analyzed by atomic force microscopy, water contact angle and Raman spectroscopy, respectively. The transmittance, antifogging and antifrosting properties of the coatings were measured. Results showed that the prepared coatings containing PVA-g-Tre with different trehalose-grafting ratios had low surface roughness with high transmittance. Compared with the PVA coating, the PVA-g-Tre coatings exhibited excellent antifogging and antifrosting properties due to the enhanced hydrophilicity and wettability by introduction of trehalose.

    Self-floating Porous PVDF-CNT Microbeads for Highly Efficient Solar-driven Interfacial Water Evaporation
    LIANG Pingping, LIU Shuai, LI Hongyi, DING Yadan, WEN Xiaokun, LIU Junping, HONG Xia
    2021, 42(8):  2689-2693.  doi:10.7503/cjcu20210045
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    Self-floating porous polyvinylidene fluoride-carbon nanotube(PVDF-CNT) microbeads were prepared by a convenient phase inversion method for solar-driven interfacial water evaporation. The unique composition and porous microsphere structure synergistically contribute to efficient sunlight capture, adequate water transport and rapid vapor escape. The higher the content of CNTs is, the better performance the PVDF-CNT microbeads show. The highest light absorption of PVDF-CNT microbeads can reach up to about 94.5% and the water surface temperature quickly rises from 20.8 ℃ to 43.1 ℃ within 2 min illumination. Under the simulated solor irradiation of 1 kW/m2, the PVDF-CNT microbeads exhibit a water evaporation rate of 1.501 kg/(m2·h) and a solar energy conversion efficiency of 94.2%.

    Graphene Oxide/Polyimide Composites with High Energy Storage Density Based on Multilayer Structure
    ZHU Deshuai, ZHAO Jianying, YANG Zhenghui, GUO Haiquan, GAO Lianxun
    2021, 42(8):  2694-2700.  doi:10.7503/cjcu20200882
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    A variety of multi-layer nanocomposite films composed of both high insulation polyimide(PI) layer and high dielectric constant graphene oxide/polyimide(GO@PI) composite layer were fabricated through layer by layer coating. The GO content and layered structure of the dielectric layer were adjusted to make the multilayer composite films with high dielectric constant and high breakdown strength. The results showed that the energy storage density of tri-layer PI/1.0 GO@PI/PI composite film was 1.27 J/cm3 at 261.5 kV/mm. Compared with the mono-layer 1.0 GO@PI film, the breakdown strength and energy storage density of the tri-layer PI/1.0 GO@PI/PI composite film were increased by 97% and 144%, respectively. Meanwhile, the dielectric loss of the composite film remained at a relatively low level(tanδ=0.0079). The composition of insulating layer and high dielectric layer afforded the synergistic effect to remedy the energy density of the multilayer composite film. The multi-layer structure strategy is benefical to the application of graphene oxide/polyimide composites in dielectric energy storage filed.