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10 October 2021, Volume 42 Issue 10

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Cover and Content of Chemical Journal of Chinese Universities Vol.42 No.10(2021)

2021, 42(10):  2. 

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Review

Recent Progress on High⁃rate Niobium-based Oxides Anode Materials

YE Yihua, BA Deliang, LIU Shuailei, CHEN Yinglin, LI Yuanyuan, LIU Jinping

2021, 42(10):  3005-3023.  doi:10.7503/cjcu20210511

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Lithium-ion energy storage devices have shown great potential in the fields of large-scale energy storage and new energy vehicles due to their high energy density and environmental friendliness. However， due to the unsatisfactory electrochemical kinetics and safety issue at high rates of traditional anode materials such as graphite and silicon， lithium-ion batteries cannot meet the current increasing requirements of fast charging and discharging. Therefore， it is significant to develop anode materials with fast insertion/de-insertion kinetics of lithium ions， excellent safety and good stability. Compared with traditional anode materials， niobium-based oxides have the advantages of suitable theoretical capacity， safer working potential and fast ion transport channels. This review summarizes the latest progress on niobium-based oxide anode materials for ultrafast lithium ion storage devices， focusing on the lithium storage mechanism and various modification strategies of niobium-based oxides. In the end， the future development directions and challenges of niobium-based oxide materials will be presented.



Recent Advances on Hydrocarbonylation of Unsaturated Hydrocarbons by Involving Carbon Monoxide

WANG Peng, LIU Huan, YANG Da

2021, 42(10):  3024-3039.  doi:10.7503/cjcu20210367

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Carbonylation of unsaturated hydrocarbons refers to the insertion of carbon monoxide（CO） into olefins（or alkynes） and different nucleophiles in the form of carbonyl group， which higher value-added chemicals are synthesized in the presence of transition metal catalysts. In this paper， the importance of carbonylation reaction in the synthesis of high value-added chemicals was briefly introduced：（1） the synthetic route was simple and the target products could be synthesized in one step with high yield；（2） the starting materials of carbonylation reaction were cheap and various， such as natural fossil oils， petrochemical and coal chemical products etc.（3） Because the raw materials were cheap and the products were more useful， the economic benefit was considerable. Then the application of several different types of carbonylation reactions（hydroformylation， hydroesterification， aminocarbonylation， hydrocarboxylation） in the development of new catalyst systems and efficient synthesis of target products were introduced. A variety of high value-added products like aldehyde， ester， amide or carboxylic acid were synthesized with high regio/chemoselectivity. Finally， the existing problems of carbonylation reaction and the future development direction and trend were prospected： （1） the application of cheap metal catalysts in carbonylation reaction； （2） developing more carbonylative substitutes on the basis of existing carbon monoxide surrogates； （3） carbonylation of some special olefins（1，3-dienes） to synthesize target compounds with high efficiency and regio/chemoselectivity； （4） explore the mechanism of carbonylation reaction process etc. It is expected to achieve the goal of green， cheap and recyclable carbonylation to produce high value-added carbonylative chemicals with high efficiency and selectivity.

? Supported by the National Natural Science Foundation of China（No.21901250） and the General Programs of China Postdoctoral Science Foundation（No.2019M651625）.



Inorganic Chemistry

Using Human Serum Albumin Nanoparticle as Carrier for co-Delivery of Ru（Ⅲ） Complex and All-trans-retinoic Acid and Its Application for Anti-Metastasis Therapy

DING Xin, SHI Hongdong, LIU Yangzhong

2021, 42(10):  3040-3046.  doi:10.7503/cjcu20210379

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Cancer is one of the main diseases threatening human life and health. Approximately 9.96 million people die from cancer each year in the world. More than 90% of cancer deaths are caused by metastasis. Therefore， the development of effective anti-metastasis drugs is of great significance for cancer treatment. In this paper， a nano-drug system based on human serum albumin（HSANP） was designed and synthesized to co-deliver Ru（Ⅲ） complex and all-trans-retinoic acid（ATRA） for anti-metastatic therapy. Ru-ATRA-HSANP shows excellent stability under water and physiological conditions and could be effectively internalized by cells. It has weak cytotoxicity， but exhibits excellent anti-metastatic effects. In conclusion， an anti-metastatic nanomedicine with good stability and low-toxicity have been constructed， which could be used for anti- metastasis therapy.



Synthesis and Anisotropic Proton Conduction of Porous Organic Salt Single Crystal

LI Hongbin, ZHANG Shuai, LI Zheng, DING Changjiang, BEN Teng

2021, 42(10):  3047-3053.  doi:10.7503/cjcu20210233

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Crystalline porous organic salt（CPOS-10） with regular morphology and large size was synthesized by ionic bonding of cis，cis-1，3，5-triaminocyclohexane·3HBr and 1，2，4，5-benzenetetracarboxylic acid at room temperature， which had good thermal stability and permanent porosity. Due to the regular morphology and large single crystal size， the anisotropic proton conduction of porous organic salt single crystal was studied for the first time， and the mechanism of anisotropic proton conduction was studied combined with crystal structure. The results showed that CPOS-10 single crystal exhibited an anisotropic proton conductivity， and the concentration of water molecules played an important role in the proton conductivity of CPOS-10. The crystal surface with high concentration of water molecules in the skeleton was easier to form hydrogen bond network with polar groups to promote proton conduction， so the proton conduction through this hydrogen bond network showed higher proton conductivity. Therefore， the non-uniform distribution of water molecules in the framework was the main reason for the anisotropic proton conduction of single crystal. The exploration of the anisotropic proton conductivity for CPOS-10 single crystal is helpful to explore the proton conduction mechanism in porous organic salts.



Analytical Chemistry

Laser-mediated Enrichment Based Surface Enhanced Raman Analysis

TANG Wentao, LI Shengkai, WANG Shen, CHEN Long, CHEN Zhuo

2021, 42(10):  3054-3061.  doi:10.7503/cjcu20210153

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Surface enhanced Raman scattering（SERS） technique has extensive application prospects in biochemical analysis and environmental monitoring field owing to its high sensitivity， low background inter- ference， superior anti-photobleaching and anti-photocarbonization capabilities， as well as ability to reflect the inherent molecular fingerprint information of the analyte. Non-target analytes are competitively adsorbed on the surface of the SERS substrate， making the analysis of trace analytes in complex systems extremely challenging. Based on the self-assemble of the graphene-isolated Au nanocrystal（GIAN） with excellent SERS performance at H₂O-Organic phase interface， the large partition coefficient of the analyte in organic phase， and GIAN can combine with the analyte viaπ-π interaction， a laser-mediated highly-efficient analyte enrichment strategy is proposed and trace SERS analysis of 9，10-bis（phenylethynyl）anthracene（BPEA） molecules is eventually realized in this work. The proposed novel analyte enrichment strategy avoids the signal fluctuation caused by the “coffee ring effect” to a certain extent and is expected to provide a reliable platform for SERS analysis of trace analytes in complex systems.



Glucose-6-phosphate Functionalized Hydrophilic Magnetic Probe： a Dual-purpose Affinity Material for Effective Separation and Enrichment of Glycopeptides/Phosphopeptides

WANG Baichun, YUAN Yuxin, YAN Yinghua, DING Chuanfan, TANG Keqi

2021, 42(10):  3062-3070.  doi:10.7503/cjcu20210256

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Glucose-6-phosphate（G6P） functionalized hydrophilic magnetic probe Fe₃O₄@PDA@TiO₂@G6P was constructed by the layer-by-layer modification on the surface of the magnetic core Fe₃O₄. Polydopamine（PDA） not only enhanced the hydrophilicity of the probe， but also acted as the coupling linker for the further grafting of titanium dioxide（TiO₂）. In addition to serving as the anchor point of G6P， the grafted TiO₂ could also effectively enrich phosphopeptides through the metal oxide affinity chromatography technology. The functionalization of G6P gave the nanospheres a highly hydrophilic surface and used the hydrophilic interaction liquid chromatography technology to achieve the goal of capturing glycopeptides. The results showed that this dual-purpose affinity probe had a low detection limit（0.1 fmol/μL）， a high selectivity［m（HRP）∶m（BSA）=1∶1000］， a good repeatability（ten cycles） and a high loading（300 mg/g） for glycopeptides. Besides， as for phosphopeptides， the obtained G6P functionalized hydrophilic magnetic probe exhibited a low detection limit（0.02 fmol/μL） and a high selectivity［n（β-casein）∶n（BSA）=1∶1000］. At the same time， this dual-purpose affinity material had the ability to simultaneously enrich glycopeptides and phosphopeptides， and 34 glycopeptides and 36 phosphopeptides were identified from human saliva， indicating that it will show great application prospects in proteomics analysis of a variety of post-translational modifications.



Rhodamine Fluorescent Probe for Tumor Targeted Hypoxia-imaging as Intra-operative Navigators

WANG Mengmeng, LUAN Tianjiao, YANG Mingyan, LYU Jiajia, GAO Jie, LI Hongyu, WEI Gang, YUAN Zeli

2021, 42(10):  3071-3081.  doi:10.7503/cjcu20210316

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Determination of tumor boundary during surgery has a great significance to achieving precise resection. The level of tumor hypoxia is closely related to the local concentration of reducing substances such as azobenzene reductases（azoreductases， AzoR， an important class of biocatalysts in solid tumor）， AzoR is able to reduce the nitrogen double bond（—N=N—） of azobenzene compounds to generate anilines. Therefore， the characterization might serve as optical AzoR probe during image-guided surgery， which exhibits wide range of application prospects in biomedicine field. In order to obtain a probe for tumor hypoxia fluorescence image-guided surgery with good targeting， low toxicity， good biocompatibility and high specificity， based on the molecular cleavage of azobenzene induced by azoreductase hypoxia and the good fluorescence performance of rhodamine， an “Off-On” type tumor with a specific response to near-infrared azohypoxia was prepared and characterized by chemical coupling. Then we confirmed its fluorescence “Off-On” performance and response mechanism from the molecular level； at the level of L02， 4T1， HeLa， and A549 tumor cells， the toxicity of the tested cell lines and the imaging performance on different hypoxia periods was also investigated. Next， 4T1 tumor model was further constructed， and the performance of tumor in situ injection and tail vein injection fluorescence imaging were studied respectively. Furthermore， the performance of fluorescence imaging-mediated surgery of tumors was further explored. On this basis， the biological safety performance was investigated. The results show that this rhodamine azo probe has high target-specific tumor hypoxia responsiveness and excellent fluorescence imaging-mediated tumor surgery potential， combined with its good photophysical properties， controlled administration time， and biological security， which is expected to provide new research tools for biomedical fluorescence imaging-mediated tumor resection.



Sampling of Ammonium Ion in High Salinity Waters Using Diffusive Gradients in Thin Films Technique

FENG Zhongmin, YANG Lan, SUN Ting

2021, 42(10):  3082-3090.  doi:10.7503/cjcu20210147

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Eutrophication is directly related to the concentration of ammonium ion. A new diffusive gradients in thin film（DGT） technique， using sodium cobalt hexacyanoferrate， was developed and evaluated for sampling ammonium ion in high salinity waters. Sodium cobalt hexacyanoferrate was prepared using double-dropwise addition method and characterized by means of SEM， XRD and nitrogen adsorption-desorption analysis. The adsorption rate and capacity for ammonium ion by sodium cobalt hexacyanoferrate and the effects of time， pH and co-existing ions on the sampling of ammonium ion by DGT devices based on sodium cobalt hexacyanoferrate were investigated. The adsorption process reached equilibrium after 60 min and was fitted well with pseudo-second-kinetic rate model. The adsorption capacity was 90.00 mg/g at the initial concentration of ammonium ion of 300 mg/L. Langmuir and Freundlich models could both fit well the adsorption behavior. The binding gel could be eluted by 1 mol/L KCl and the elution efficiency was 85.68%（n=6）. The uptake mass of ammonium ion by DGT device as a function of time over 24 h demonstrated excellent linearity（r²=0.994）. The uptake mass of ammonium ion was quantitative over pH range 4—8 and typical ion concentration ranges（up to Na⁺ 10000 mg/L， K⁺ 25000 mg/L， Mg²⁺ 20000 mg/L， Ca²⁺ 25000 mg/L）. The results demonstrate that the DGT devices based on sodium cobalt hexacyanoferrate can accurately adsorb ammonium ion in high salinity waters.



Organic Chemistry

Cationic Covalent Organic Frameworks for the Enhanced Removal of Non-steroidal Anti-inflammatory Drugs from Water

YAN Yanhong, LI Shuqing, TANG Xihao, ZHENG Shengrun, CAI Songliang, ZHANG Weiguang, GU Fenglong

2021, 42(10):  3091-3098.  doi:10.7503/cjcu20210417

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1，3，5-Triformylphloroglucinol（TFP） and ethyl bromide（EB） were used as building blocks to synthesize a two-dimensional β-ketoenamine-linked cationic covalent organic framework（COF）， namely TFP-EB COF， under solvothermal conditions. The obtained TFP-EB COF exhibits good crystallinity， high specific surface area and abundant ethidium bromide units， thus it can be applied as the adsorbent for the removal of non-steroidal anti-inflammatory drugs（NSAIDs） from aqueous solutions. Interestingly， the cationic TFP-EB COF can adsorb anionic NSAIDs such as diclofenac sodium（DCF-S） and p-aminosalicylate sodium（PAS-S） in water with fast adsorption kinetics and high adsorption capacity. The maximum adsorption capacities of TFP-EB COF for DCF-S and PAS-S are found to be 350.4 and 145.3 mg/g， respectively. In sharp contrast， the neutral TFP-BND COF synthesized by TFP and 4，4'-diaminobiphenyl（BND） under similar conditions shows poor adsorption ability toward DCF-S and PAS-S with maximum adsorption capacities of only 59.7 and 13.6 mg/g， respectively. The more excellent adsorption performance of TFP-EB COF than TFP-BND COF can be ascribed to the presence of strong electrostatic interaction between the EB units anchored in the TFP-EB COF channels and the carboxylate groups in NSAIDs. In addition， the ion competing experiments and cyclic regeneration experiments were also carried out， which demonstrate the great potential application of cationic TFP-EB COF in the removal of NSAIDs.



Host-guest Complexation Behavior of Nardosinone and Water-soluble Phosphate Salt Pillar［6］arene

YANG Ju, SU Lijiao, LI Canhua, LU Jiajia, YANG Junli, GU Jie, YANG Li, YANG Lijuan

2021, 42(10):  3099-3106.  doi:10.7503/cjcu20200897

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Using water-soluble phosphate salt pillar［6］arene（WP6P） as the host and the natural drug nardosinone（ND） as the guest， the saturated solution method was used to construct a new the host-guest inclusion compound of ND/WP6P. The complexation behavior between the host and guest was studied by UV spectrome- tric titration. The results showed that ND and WP6P formed inclusion compound at a molar ratio of 1∶1， and the complex constant was 5.160×10⁴ L/mol. Infrared spectroscopy（IR）， X-ray powder diffraction（XRD）， thermos gravimetry（TG）， differential thermal analysis（DSC） and scanning electron microscope（SEM） were used to characterize the ND/WP6P inclusion compound. The possible inclusion mode of between ND and WP6P was further verified by nuclear magnetic resonance（¹H NMR， 2D NMR） and molecular docking simulation. This study provides a theoretical reference for the application of water-soluble pillar［6］arene in natural medicine.



Interfacial Behaviors of Bio-based Surfactant Escin

ZHENG Zirui, LI Zilu, ZHAO Kefei, WU Tianyue, ZHANG Chenhui, GAO Yuxia, DU Fengpei

2021, 42(10):  3107-3115.  doi:10.7503/cjcu20210536

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The interfacial behaviors of natural triterpene saponin escin at gas-liquid， liquid-liquid， and solid-liquid interfaces were investigated by Wilhelmy method， pendant drop method， and high-speed camera dynamic shooting method， respectively. The properties of the emulsion prepared with escin as the emulsifier and the regulation of escin on droplet impact behavior on hydrophobic solid surface were investigated， and the mechanism were analyzed from molecular level. The results showed that escin could be adsorbed at the air- water interface， and the surface tension of water was reduced to 42.1 mN/m with the critical micelle concentration of 5×10^?4 mol/L. In addition， escin molecules can also be adsorbed at the oil-water interface， inserting the hydrophobic skeleton into the oil phase and the hydrophilic headgroup into the water phase to form a stable interfacial film， finally reducing the interfacial tension. With the increase of the concentration， the emulsion prepared with escin as the emulsifier could achieve smaller particle size， larger Zeta potential， and showed good stability in a short period of time. Moreover， the bounce and retraction of droplet on hydrophobic solid surface could be obviously inhibited by escin with higher concentration， leading to good spreading， which is conducive to its application in many fields.



Physical Chemistry

Mechanism of Ion Transport Across Membranes Assisted by Molecular Shuttles

MIAO Mengyao, GUO Yichang, SHAO Xueguang, CAI Wensheng

2021, 42(10):  3116-3124.  doi:10.7503/cjcu20210483

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The mechanism of K⁺ transmembrane transport assisted by a rotaxane-based molecular shuttle was studied by advanced enhanced sampling molecular dynamics simulations. The rotaxane consisted of an amphiphilic axel， a large crown ether wheel sliding on the axle， and a linked small crown ether carrier. There were three positively charged binding sites on the axel. By calculating the free-energy change of the shuttle process， the effects of solvents（chloroform， acetonitrile， water， and chloroform-acetonitrile） and the middle binding site on the shuttle movement of the rotaxane were explored. Furthermore， the important role of the middle bin- ding site in transmembrane ion transport across cell membranes（using water-chloroform-water to simulate） was analyzed. The results indicate that changing the solvent does not alter the movement mode of the rotaxane （without K⁺）， but as the polarity of the solvent increases， the free energy barrier against the shuttle significantly decreases. In the chloroform-acetonitrile mixed solvent， the protonation state of the middle binding site does not affect the free energy barrier against shuttling of the rotaxane（without K⁺）. However， in the environment of the simulated cell membrane， compared with deprotonation， the protonation of this binding site significantly decreases the free energy barrier of shuttling and facilitates the transport of the K⁺ across the membrane， indicating that the protonation of the middle binding site is paramount importance for ion translocation. Further analysis shows that the cooperation between the shuttling movement of the large ring and the swinging movement of the small ring constitutes another key factor in accelerating transmembrane ion transport.



Adsorption Reduction of Hexavalent Chromium and co-Catalytic Degradation of Organic Pollutants by Carbon Doped Hexagonal Boron Nitride Supported MoS₂

CUI Jinping, CHEN Wenxian, YU Feifan, CAO Shiyu, LYU Weiyang, YAO Yuyuan

2021, 42(10):  3125-3134.  doi:10.7503/cjcu20210429

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Aiming at the problem of the low Cr（Ⅵ） removal capacity of molybdenum disulfide（MoS₂） due to easy agglomeration， dopamine was used to modify hexagonal boron nitride（BN） with excellent adsorption and chemical stability， and then the carbon doped hexagonal boron nitride supported MoS₂ nanocomposite （c-BN@MoS₂） was obtained by calcination and hydrothermal method， improving the dispersion of MoS₂ in the composite materials. The performance of c-BN@MoS₂ on the adsorption and reduction of Cr（Ⅵ） and the synergistic catalytic degradation of organic pollutants were deeply investigated at room temperature. The experimental results indicated that the adsorption reduction removal rate of Cr（Ⅵ） at 50 mg/L by c-BN@MoS₂ was more than 95% within 40 min. The maximum capacity for Cr（Ⅵ） removal could reach 401 mg/g under pH of 2.0 at 25 ℃， which was obviously higher than that of Cr（Ⅵ） by MoS₂（98 mg/g）. This may be attributed to the fact that the introduction of c-BN increased the specific surface area and average pore diameter of MoS₂， promoting the formation of 1T phase of MoS₂， which is conducive to the adsorption of Cr（Ⅵ） and accelerating the electron transfer in the redox process. When c-BN@MoS₂ was introduced into the Fe²⁺/PMS system， the degradation performance of sulfamethoxazole was significantly enhanced， and its reaction rate constant was 4 times as high as that of the Fe²⁺/PMS system， which was mainly due to the fact that c-BN@MoS₂ significantly accelerated the transition from Fe³⁺ to Fe²⁺， resulting in more ·OH production， thereby achieving the enhancement effect of pollutants degradation. This paper opens up a new direction for the treatment of heavy metals and organic pollutants in wastewater by hexagonal boron nitride， and provides a useful reference for the efficient treatment of wastewater pollution.



High-throughput Virtual Screening of CDK2/Cyclin A2 Target Inhibitors

YE Chenghao, LIANG Heng, LI Enmin, XU Liyan, LI Peng, CHEN Guanghui

2021, 42(10):  3135-3143.  doi:10.7503/cjcu20210405

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Abnormal expression of CDK2/Cyclin A2 protein is closely related to the occurrence of breast cancer， oral cancer， and esophageal squamous cell carcinoma. The binding pocket of CDK2/Cyclin A2 complex protein is different from that of CDK2 monomer. So far， no inhibitor that targeting CDK2/Cyclin A2 protein has been approved clinically. In order to obtain the high-efficiency inhibitor towards CDK2/Cyclin A2， the high-throughput virtual screening was performed among approximately 900000 molecules based on the three databases including DrugBank， ChEMBL and TCM@Taiwan. The 10 inhibitor molecules reported experimentally were used for pharmacophore models， to screen for hit molecules in above databases by means of docking， ADME， clustering analysis， toxicity prediction. Furthermore， 3 lead molecules including DrugBank-2004， DrugBank-583 and ChEMBL-7122 were screened out after moleculor dynamics（MD） simulation， bin- ding free energy calculation and average non-covalent interaction（aNCI） analysis， which are superior to Roscovitine because of the stronger electrostatic interaction. Moreover， as the result of the larger binding pocket than CDK2， the moderation of repulsion between lead molecules and target residues of Lys33， Asp86， Lys129 and Asp145 is achieved， and thus leading to greater binding free energies. The present work will provide a theoretical basis for the experimental research in the future.



Tunable Enantioselective Adsorption of the As⁃synthesized Mesoporous Silica Through Chiral Imprinting

SONG Wenyao, ZHOU Zhanglang, YANG Xinli, CHEN Lan, GE Guanglu

2021, 42(10):  3144-3150.  doi:10.7503/cjcu20210401

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Chiral mesoporous silica（CMS） has unique chiral structure and good enantioselective adsorption properties， which can be used for the separation of racemic mixtures. The preparation and applications of the CMS have received many attentions in recent years， while less research has been conducted on the origin for the chiral selective adsorption of the CMS. In this work， CMS was prepared using chiral anionic surfactants as supramolecular templates assisted by co?structure directing method. The enantioselective adsorption of racemic molecules and chirality for the CMS were measured using circular dichroism（CD）， and the effect of mesoporous surface modification with or without co?structure directing agent TMAPS（N?trimethoxysilylpropyl?N， N， N?trimethylammonium chloride） on the adsorption selectivity was compared. As a result， the as?synthesized CMS whose inner surface is grafted with TMAPS induced by supramolecular templates with opposite chirality can produce chiral imprinting with opposite helical arrangement and thus result in opposite adsorption selecti?vity. It has been confirmed that the enantioselective adsorption of the CMS for separating racemic mixtures is mainly caused by the chiral imprinting of TMAPS with helical arrangement grafted on the mesoporous surface. The chiral supramolecular templated TMAPS alignment to produce chiral imprinting is practical for some applications， which can in situ tune the enantioselective adsorption and separation property for the as?synthesized mesoporous materials. This work is thought to widen the applications of the CMS in many areas such as stereoselective recognition， asymmetric catalysis and drug delivery etc.



Screening of Deep Eutectic Solvent Based on Efficient Recovery of Spent Lithium⁃ion Battery Cathode Materials

GONG Shanshan, WU Tong, WANG Guange, HUANG Qing, SU Yuefeng, WU Feng

2021, 42(10):  3151-3159.  doi:10.7503/cjcu20210372

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To resolve the secondary pollution and high energy consumption caused by the recycling of spent lithium-ion batteries（LIBs）， a green and efficient method for leaching valuable metals from spent LIBs cathode materials is developed. Choline chloride and different hydrogen bond donors（oxalic acid， malonic acid， glutaric acid and benzenesulfonic acid） were used to synthesize choline chloride/acid binary deep eutectic solvent（DES）， chlorine choline/acid/H₂O and choline chloride/acid/ethanol ternary DES. The formation process of the hydrogen bond between choline chloride and acid was characterized by means of Fourier transform infrared spectroscopy（FTIR） and nuclear magnetic resonance spectroscopy（NMR）. The impacts of carboxylic acid alkyl chain length， acidity and addition of water and ethanol on the leaching of spent LiCoO₂ were investigated. The results show that the leaching capacity of DES decrease with the increase of the carboxylic acid alkyl chain length. The acidity of the acid cannot be concluded as the main reason for the higher ability to dissolve metal oxides. The equimolar addition of water has little effect on the leaching efficiency of DES， while the equimolar addition of ethanol will affect the hydrogen bond structure of DES， which has a greater impact on the leaching efficiency. At last， choline chloride/benzenesulfonic acid/ethanol DES was screened as a green and efficient leaching agent for spent LiCoO₂， leaching efficiencies of Li and Co were as high as 98.6% and 95.2%， respectively.



Synthesis of ZnIn₂S₄/g-C₃N₄ Nanocomposites with Efficient Photocatalytic H₂ Generation Activity by a Simple Hydrothermal Method

SUN Yaguang, ZHANG Hanyan, MING Tao, XU Baotong, GAO Yu, DING Fu, XU Zhenhe

2021, 42(10):  3160-3166.  doi:10.7503/cjcu20210365

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ZnIn₂S₄/g-C₃N₄ composites were prepared by a simple hydrothermal method and characterized by means of X-ray diffraction（XRD）， Fourier transforms infrared spectroscopy（FTIR）， UV-Vis diffuse reflectance spectroscopy（UV-Vis DRS）， transmission electron microscopy（TEM）， and fluorescence spectroscopy（PL）. The results show that when the loading capacity of ZnIn₂S₄ is 20%（mass fraction）， the composite shows the best performance of photocatalytic hydrogen production， and the rate of hydrogen production can reach 637.08 μmol ·g^-1·h^-1， which is 4 times and 37 times of pure ZnIn₂S₄ and pure g-C₃N₄， respectively. The reason is that ZnIn₂S₄/g-C₃N₄ has a tight heterojunction interface， which improves the energy band matching and interfacial charge transfer of the components， thus effectively enhancing the separation and transport of charge carriers， and improving the photocatalytic performance.



Fabrication of Triphase Enzyme Electrode Based on Porous Gold Substrate for High-performance Electrochemical Biosensor

ZHANG Jiayi, DING Zhenyao, WANG Dandan, CHEN Liping, FENG Xinjian

2021, 42(10):  3167-3174.  doi:10.7503/cjcu20210355

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The interface microenvironment is the key factor affecting the enzymatic reaction and enzyme biosensing performance. In this study， we fabricated an oxidase enzyme electrode with an air-liquid-solid triphase interfacial microenvironment by adjusting the surface wettability of three-dimensional（3D） micro/nano- structured porous gold substrate， and studied the effects of interfacial microenvironment on enzymatic reaction kinetics and performance of enzyme electrode. Based on the triphase interface porous gold structured enzyme electrode， the reactant oxygen can be directly and quickly transferred from the gas phase to the enzyme reaction interface， which greatly increases the interface oxygen concentration and stability， thus enhances the oxidase activity and the stability of enzyme electrode response. Take glucose as a model analyte， we found that the electrochemical enzyme biosensor has a wide linear range， high sensitivity， low detection limit and good stability. This unique triphase reaction interface design strategy provides a new idea for the construction of high-performance enzyme biosensor and accurate detection of biomolecules.



Comprehensive Thermodynamic Model and Polythermal Phase Diagram Prediction of Nitrate Type Brine Systems

WANG Xingfan, ZHOU Huan, ZHOU Kuo, JIN Fenli, YANG Junfang

2021, 42(10):  3175-3186.  doi:10.7503/cjcu20210334

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Nitrate type aqueous electrolyte systems are encountered in salt lake brine， nitrate industries and wastewater treatment. Due to the high solubility of nitrate， it is still challenging to achieve accurate thermodynamic expression of physical properties and phase equilibrium of nitrate complex electrolyte system. The Na⁺//NO₃^-， Cl^-， SO₄^{2 -} -H₂O typical system of coal chemical wastewater was selected as the research object. Based on the improved eNRTL model， the comprehensive thermodynamic model of electrolyte system was composed of activity coefficient model， liquid properties model， species thermodynamic data model， and solid-liquid phase equilibrium model. Based on the freezing points， saturated vapor pressure， isobaric molar heat capacity， activity coefficients and osmotic pressure coefficients of binary systems and the isothermal phase equilibrium data of ternary systems， 12 sets of liquid parameters and thermodynamic parameters of 7 solid species were obtained by multi-objective fitting. The complete multi-temperature phase diagrams of 3 binary systems， 3 ternary systems and one quaternary system were calculated and predicted. The applicable temperature reached all the experimental temperature ranges， namely， 254.65—543.15 K， and the applicable concentration reached saturation， the concentration of NaNO₃ reached 226.88 mol/kg. The predicted results of multi temperature phase diagrams of ternary and quaternary systems are in good agreement with the experi- mental data. The results expand the expression ability of electrolyte model in ultra-concentrated and multi- temperature complex systems， and the model and parameters can be used in chemical process of nitrate- containing system， wastewater treatment， salt lake brine resource development and other processes.



Crystal-like Hydrogels Consisting of Parallel Hexahedrons Obtained from the Self-assembly ofβ⁃Cyclodextrin/perfluorononanoic Acid Inclusion Complexes

ZHANG Juan, HU Xinyue, WANG Hongbo, LIAN Ying, LE Jinyu, YANG Zihao

2021, 42(10):  3187-3194.  doi:10.7503/cjcu20210320

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The inclusion complexes formed from cyclodextrins（CDs） and surfactants have been found to assemble into various aggregates and play important roles in supramolecular self-assembly. The self-assembly of β-cyclodextrin（β-CD）/perfluorononanoic acid（PFNA） system was investigated in solution. The phase diagram was obtained by changing the mixed ratio and total concentration of β-CD and PFNA. Interestingly， the hydrogels had crystal-like structure and were composed of inerratic parallel hexahedrons with the thickness of several nanometers and the length of more than a dozen microns. Based on the experimental results， the formation mechanism of the hydrogel was proposed： PFNA molecules were included by β-CD to form β-CD@PFNA complexes， which then piled into highly-ordered channels with the form of “head to head， tail to tail” of β-CD molecules. Then these channels were stacked tightly induced by hydrogen bonds and crystallized into parallel hexahedrons. These hexahedrons were cross-linked to form a three-dimensional network that wrapped the solvent to form hydrogels. This self-assembly strategy based on host and guest interaction of fluorocarbon surfactants and cyclodextrins is expected to provide a new idea for controlled self-assembly of novel aggregates.



Polymer Chemistry

Low-temperature Impact Behavior of Droplet on Injection-compression Molded Nanostructured PP/POE Blend Surfaces

HUANG Huilong, HUANG Hanxiong

2021, 42(10):  3195-3202.  doi:10.7503/cjcu20210404

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An anodic stainless steel template was prepared by two-step anodic oxidation. Using injection- compression molding with the template， replicas with the nanopillars on their surfaces were molded for flexible polypropylene/poly（ethylene-co-octene）（PP/POE） blend with a mass ratio of 3∶1 and quasi-rigid PP. The dynamic behavior of the droplets impacting the replicas with ?10 ℃ was investigated. It was demonstrated that the dense nanopillars endowed the replica surfaces with superhydrophobicity and extremely low adhesion. In a lower impact velocity range， the contact times of the droplets impacting on the blend replica surface were shorter than those on the PP replicas. This is attributed to the conversion of the elastic potential energy within the flexible nanopillars stored in the spreading stage to the kinetic energy of the droplets in the retraction stage. In a higher impact velocity range， the contact time of the droplets on the blend replica surface was further shortened when the elastic potential energy stored within both replica substrate and nanopillars was converted into the kinetic energy of the droplets. The results suggest that the flexibility and surface superhydrophobicity of the PP/POE replica endow it with excellent anti-freezing adhesive properties. Compared with the PP counterpart surface， the freezing time of the droplet（50 μL） was extended by 2.71 times and the ice adhesion strength was reduced by 58% on the PP/POE blend replica surface. The results demonstrate that it is feasible to rapidly and massively mold flexible superhydrophobic polymer surfaces with anti-freezing adhesive/anti-icing function.



Living Ring-opening Polymerization of O-Carboxyanhydrides Catalyzed by Pyridine Derivatives

LI Chen, LI Yuesheng

2021, 42(10):  3203-3210.  doi:10.7503/cjcu20210315

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Poly（α-hydroxy acid）s can be synthesized by ring-opening polymerization（ROP） of O-carboxyanhydrides（OCAs） derived from α-hydroxy acids with rich side groups， which make up for the defects of poly（lactic acid） with restricted structure and performance. However， in the process of OCA ring-opening polymerization， chiral α-H is prone to racemization， which leads to the decrease of the stereoregularity of the polymer. Here， a high performance organic catalyst with simple structure， 4-methoxypyridine， is capable of rapid catalyzing the living ROP of OCA under the mild conditions， and effectively inhibits the side reactions of transesterification and racemization of chiral α-H to synthesize narrowly distributed poly（α-hydroxy acid） with high stereoregularity. In addition， although the ROP of OCA in common solvents such as toluene and tetrahydrofuran shows first-order kinetics， that in epoxy solvents follows 0-order kinetics， and the polymerization rate is independent of the monomer concentration. As a novel and efficient Lewis base catalyst， 4-methoxypyridine exhibits a great potential application value in the efficient synthesis of multi-block degradable polyester and preparation of polyester biological pharmaceutical carriers.



Preparation and Properties of Light-weight Flexible Polyimide Paper-based Electromagnetic Shielding Composites

ZHANG Ruqiang, ZHANG Guoliang, LONG Zhu, ZHANG Dan, LI Zhiqiang, WANG Shihua, HU Ailin

2021, 42(10):  3211-3217.  doi:10.7503/cjcu20210249

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Nickel/polypyrrole@polyimide fiber paper-based electromagnetic shielding composites（Ni/PPy@ PI-CP） with sandwich structure were prepared by means of polyimide fiber paper-based conductive framework via vapor deposition of polypyrrole（PPy） and palladium-free electroless plating on PI-CP. Its morphology， electrical conductivity， mechanical properties and electromagnetic shielding performance were characterized， and the effects of temperature， bending degree， and folding times on the electrical conductivity and electromagnetic shielding performance of Ni/PPy@PI-CP were investigated. The results show that the electromagnetic shielding performance of Ni/PPy@PI-CP-3 can reach more than 70 dB； Ni/PPy@PI-CP-3 exhibits excellent conductivity stability under bending deformation， and its conductivity loss can be ignored. Even after 200 times of repeated folding tests， the conductivity of Ni/PPy@PI-CP-3 remains around 92.4%. In addition， Ni/PPy@PI-CP-3 has the characteristics of light weight， easy processing， and has stable thermal properties， its electromagnetic shielding performance after 300 ℃ treatment is still maintained at more than 80%.



Materials Chemistry

Effect of Hollow Multi-shelled TiO₂ on Mechanical Properties of Epoxy Resin Composites

WANG Peng, MAO Dan, WAN Jiawei, QI Qi, DU Jiang, WANG Dan

2021, 42(10):  3218-3224.  doi:10.7503/cjcu20210378

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In order to improve the mechanical properties of epoxy resin（EP）， TiO₂ hollow multi-shelled structures （HoMSs） were synthesized by sequential templating approach， and then coupling agents were used to graft the obtained HoMSs. After that， the modified TiO₂ HoMSs were filled into the EP to prepare TiO₂ HoMSs/EP composites， which were compared with single-shelled TiO₂/EP composites. The effects of shell number and coupling agent modification on the mechanical properties of the composites were studied. It is demonstrated that the mechanical properties of the composites increase as the number of shells increases， and can be further improved by modifying TiO₂ HoMSs with coupling agents. The tensile strength， elongation at break and impact strength of silane coupling agent KH-560 modified triple-shelled TiO₂ HoMSs/EP composites can reach 71.66 MPa， 7.4% and 35.81 kJ/m²， respectively. Scanning electron microscopy（SEM） images exhibit that the TiO₂ HoMSs/EP composites possess the rougher cross section than that of pure EP， which illustrates that HoMSs can absorb the external stress and hinder the crack propagation to improve the toughness of the composites and enhance the impact strength of the composites.



Polydopamine-coated Fe₃O₄/methylprednisolone/cyclophosphamide Superparticles for the Magnetic Targeting Treatment of Pulmonary Fibrosis

SUN Qirui, ZHAO Nan, LIU Shuwei, XIN Hua, ZHANG Hao, ZHANG Lening

2021, 42(10):  3225-3232.  doi:10.7503/cjcu20210438

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Pulmonary fibrosis is a serious fatal disease and it exists clinical adverse effects for the conventional combined treatment using methylprednisolone（MPS） and cyclophosphamide（CTX）. In this work， polydopamine（PDA）-coated Fe₃O₄/MPS/CTX superparticles（Fe₃O₄/MPS/CTX@PDA SPs） were prepared to reduce the adverse effects of drugs， which provide a magnetic targeting strategy for the therapy of pulmonary fibrosis. In the experiment， Fe₃O₄ SPs were foremost prepared from Fe₃O₄ nanoparticles using oil-in-water droplets as the templates， and followed by coating PDA shell in the presence of MPS and CTX to produce Fe₃O₄/MPS/CTX@PDA SPs. Systematically characterizations proved the successful preparation of Fe₃O₄/MPS/CTX@PDA SPs， and revealed the stability， magnetism， drug loading and release. The cytotoxicity was further discussed in vitro， and an animal model was built to confirm the magnetic targeting of Fe₃O₄/MPS/CTX@PDA SPs in vivo.



Synthesis and Spectral Properties of Ag/SiO₂-Al₂O₃ Composite Nanomaterial Based on Molecular Sieve Template

WANG Yong, DONG Biao, SUN Jiao, DONG Delu, SUN Liankun

2021, 42(10):  3233-3239.  doi:10.7503/cjcu20210304

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Ag nanoparticles with SiO₂-Al₂O₃ amorphous structure as the protective layer have important applications in the field of sterilization and catalysis. The morphology control of Ag nanoparticles is a privotal guarantee for its excellent performance， especially the synthesis of Ag nanoparticles with regular structures has always been a difficulty in this field. In this paper， the metastable structure of SiO₂-Al₂O₃ molecular sieve was used as the template， and the ion exchange method is adopted at room temperature. The ion exchange time was adjusted to control the distribution and content of Ag in the molecular sieve. In the presence of reducing agent N（C₂H₅）₃， amorphous composite structure materials with different ratios of Ag/SiO₂-Al₂O₃ were obtained by microwave reduction reaction. The reslults of transmission electron microscopy showed that small-sized Ag nanoparticles can be distributed in the amorphous SiO₂-Al₂O₃ matrix after different proportions of precursors were reduced by microwave method. The Ag nanoparticles showed necklace-like structure and were linked and wrapped by an amorphous SiO₂-Al₂O₃ lamella when the proportion of silver was increased. This type of structure not only has the catalytic performance of Ag nanoparticles， but also shows good stability under the protection of the SiO₂-Al₂O₃ lamella. It has a wide range of application prospects in the sterilization and catalysis fields.



Preparation and Properties of Nano Lithium Magnesium Silicate-chitosan-sodium Alginate Composite Scaffold Materials

WANG Mingxia, LIU Zhihui, ZHU Zhen, LI Lingfeng, WANG Bowei

2021, 42(10):  3240-3246.  doi:10.7503/cjcu20210184

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Using vacuum freeze-drying technology， composite scaffolds were fabricated by mixing different mass fractions of nano-lithium magnesium silicate（nLMS） with chitosan and sodium alginate. Results showed that the composite scaffolds were porous solids possessing morphological plasticity， the longitudinal section of the composite scaffold was lamellar， the structure was loose and the internal pores were highly connected. With the increase of nLMS content， the porosity of the composite scaffold decreased and then increased. When the mass fraction of nLMS solution was 3%， both the swelling ratio and the degradation rate of the composite scaffold were the lowest. Besides， the addition of nLMS reduced the toxicity of the composite scaffold. The optimal mass fraction of nLMS solution to prepare the composite scaffold is 3%.