Table of Content

10 December 2021, Volume 42 Issue 12

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Contents

Cover and Content of Chemical Journal of Chinese Universities Vol.42 No.12(2021)#br#

2021, 42(12):  1-6. 

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Volume Contents of Chemical Journal of Chinese Universities to Vol.42(2021)

2021, 42(12):  1-14. 

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Review

Advances in Silicon and Silicon-based Anode Materials

HAN Muyao, ZHAO Lina, SUN Jie

2021, 42(12):  3547-3560.  doi:10.7503/cjcu20210639

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Silicon（Si） has high theoretical capacity， low voltage platform and abundant natural resources， which has the potential to become the next generation high energy density lithium ion batteries anode material. However， Si has low inherent conductivity and great volume change in the cycle process， which is different from graphite and should not be directly used as an anode material. Therefore， many modification strategies have been developed to improve or adapt to Si based anode materials from dimension structure， composites， binders and electrolytes， so as to meet the requirements of commercialization. In this paper， the research pro-gress of Si based anode materials in recent years was reviewed， the design elements of different aspects were summarized， and the performance of representative materials was introduced. Finally， the problems faced by Si based anode materials were briefly analyzed， and the research prospect of Si based anode materials as lithium ion batteries was forecasted.



Inorganic Chemistry

Effect of Zn²⁺ Substituting Ga³⁺ on Structure and Photocatalytic Properties of Wurtzite β-CuGa_1-xZn_xO₂ with Unequal Doping

YAO Mingcai, YANG Qiang, MENG Jian, LIU Xiaojuan

2021, 42(12):  3561-3570.  doi:10.7503/cjcu20210542

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Functional ceramic material with unequal doping of Zn²⁺ at the Ga-site， β-CuGa_1-xZn_xO₂， were synthesized via ion exchange method. Firstly， the crystal structure of the material was investigated by means of X-ray diffraction（XRD） and transmission electron microscopy（TEM）. Furthermore， the thermal stability of the material was studied by in?situ high temperature X-ray diffraction（HT-XRD） and synchronous thermal analyzer（TG-DSC）. Next， the optical properties of the material were assessed by UV-Vis diffuse scattering spectroscopy（UV-Vis DRS） and first principles calculations. Then， the effect of the introduction of Zn²⁺ at the Ga-site on the performance of the ceramic was evaluated by the degradation reaction of methyl orange（MO）. The results showed that the introduction of Zn²⁺ is unfavorable to the degradation reaction. Finally， the degradation mechanism was investigated by photoluminescence spectroscopy（PL）. In summary， based on the above experimental results， another possible method to improve the properties of β-CuGaO₂ is proposed.



Design and Electroluminescence Properties of Narrow-spectrum Phosphorescent Complexes

ZHANG Huidong, GU Panpan, ZHANG Fang, DU Mingxu, YE Kaiqi, LIU Yu

2021, 42(12):  3571-3578.  doi:10.7503/cjcu20210537

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Through the design and screening of cyclometalated（C^N） ligands and auxiliary ligands， a new sky blue iridium metal complex （MeFPyPy）₂Ir（dipcMePy）（MFPMP） was constructed， where the optimized proportion of ³LC and ³MLCT/³LLCT transition has been achieved. The MFPMP-based PhOLED realizes narrow spectrum， single peak， high brightness and high efficiency sky blue EL emission with a half peak width of 52 nm and a maximum emission wavelength of 476 nm， achieving an external quantum efficiency（EQE） of more than 25% at a practical luminance of 1000 cd/m²， which can be comparable to that of the highest-level OLEDs reported so far. This work provides a feasible way for further developing the phosphorescent complex materials with higher color purity and more practicability.



Inhibitory Effect of Four Kinds of Keegin-type Phosphomolybdate on Tyrosinase and Melanin Formation and Its Antioxidant Activities

SHUAI Die, ZHAO Meijuan, CHEN Bingnian, WANG Li

2021, 42(12):  3579-3588.  doi:10.7503/cjcu20210527

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Four kinds of transition metal V substituted Keggin type phosphomolybdate Na_3+nPMo_12-nVnO₄₀ （abbreviated as PMo_12-nV_n）（n=2， 3， 4， 5） were synthesized and characterized. The kinetic enzymatic method suggested that the inhibition type of four compounds on tyrosinase was reversible mixed inhibition， and the number of transition metal vanadium substitution would affect the inhibition effect of tyrosinase. When the enzyme content was 500 U/mL， the inhibition rates of PMo₁₀V₂， PMo₉V₃， PMo₈V₄ and PMo₇V₅ on tyrosinase were （7.046±0.506）， （12.128±0.574）， （12.362±0.802）， （9.860±1.490） mmol/L， respectively. The molecular docking experiment confirmed that there was hydrogen bond and van der Waals force interaction between the compound and tyrosinase. The four compounds did not produce cytotoxic effects on B16 melanoma cells， and could significantly inhibit the production of melanin. In addition， 1，1-diphenyl-2-picrylhydrazyl radical 2，2-diphenyl-1-（2，4，6-trinitrophenyl）hydrazyl（DPPH） and 2，2'-azinobis-（3-ethylbenzthiazoline-6-sulphonate）（ABTS） free radical scavenging experiments confirmed that polyoxometalates had good antioxidant capacity. What’s more， they have stronger DPPH radical scavenging ability.



Syntheses of Imidazole-coordinated Ru（II） Half-sandwich Macrocyclic Complexes and Their Anti-cancer Activity

DUAN Jun, ZHOU Pingping, ZHANG Liqian, MA Lin, YU Wen, ZHU Meiqi, ZHUANG Minyan, YANG Fenglei, CAO Changsheng, ZHANG Peng, SHI Yanhui

2021, 42(12):  3589-3599.  doi:10.7503/cjcu20210407

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A series of ruthenium（Ⅱ） rectangular macrocyclic assemblies（4—12） was synthesized by half-sandwich ruthenium（Ⅱ）（Ru1—Ru3） and 1，3-diimidazolebenzene ligands（1—3）. The composition and structure of assemblies 4—12 were determined by nuclear magnetic resonance spectroscopy， high resolution mass spectroscopy， elemental analysis and single crystal X-ray diffraction. The toxicity of these ruthenium（Ⅱ） assemblies 4—12 to four human tumor cell lines was studied by MTT experiments， and it was found that the oxalic and benzoquinone ruthenium assemblies 4—9 exhibited little cytotoxic activity against the tumor cell lines（IC₅₀>100 μmol/L）， except that naphthoquinone ruthenium assemblies 10—12 showed good cytotoxic activity against all tested tumor cell lines（IC₅₀<2.22 μmol/L）. The acute toxicity experiment of zebrafish eggs showed that the toxicity of the assembly 12 was lower， and the tumor experiment in the zebrafish showed that the assembly 12 had a better anti-cancer effect in the organism. The results showed that the main interaction between Ru assembly and DNA was insertion.



Analytical Chemistry

An Enzyme-free and Label-free Fluorescent Probe for Detection of Microcystin-LR Based on Circular DNA-Silver Nanoclusters

YANG Xinjie, LAI Yanqiong, LI Qiuyang, ZHANG Yanli, WANG Hongbin, PANG Pengfei, YANG Wenrong

2021, 42(12):  3600-3605.  doi:10.7503/cjcu20210471

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An enzyme-free and label-free fluorescence sensing method for detection of Microcystin-LR（MC-LR） was developed based on circular DNA-silver nanoclusters （circular DNA-AgNCs） fluorescent probe， which was prepared by using circular DNA as template. The circular DNA was composed of MC-LR aptamer（Apt） and aptamer complementary（cDNA）， which can be used as DNA template to synthesize AgNCs. The morphology and optical properties of prepared circular DNA-AgNCs were characterized by transmission electron microscope（TEM）， ultraviolet?visible spectroscopy（UV-Vis） and fluorescent spectroscopy（FL）. The experimental results showed that the circular DNA is dissociated due to the high specificity and affinity between Apt of circular DNA and MC-LR in the presence of object MC-LR， resulting in the releasing of cDNA-AgNCs with an enhanced fluorescent intensity at 610 nm. Under the optimized experimental conditions， the linear range of circular DNA-AgNCs fluorescent probe for MC-LR determination is 0.005—500 μg/L with a detection limit of 1.7 ng/L（S/N=3）. The developed fluorescent probe has the advantages of simple preparation， no labe-ling and high sensitivity， providing a simple， reliable and effective method for the determination of Microcystin-LR in practical environmental water samples.



Preparation of Surface Oriented Magnetically Imprinted Polymers and the Selective Recognition of Quercetin

LI Fei, LI Xiaoxuan, LI Yijun, HE Xiwen, CHEN Langxing, ZHANG Yukui

2021, 42(12):  3606-3614.  doi:10.7503/cjcu20210446

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Flavonoids are one of the most important compounds， which have been successfully used in medicine in ancient times because of their unique antioxidant and anti-inflammatory effects. Quercetin is a polyphenol compound， which contains cis-diol structure and belongs to flavonol. It is found in a variety of foods， including vegetables and fruits， such as tea， cocoa powder， cranberries， kale， celery， cauliflower， lettuce， tomatoes and carrots. Quercetin has the ability of scavenging free radicals and binding transition metal ions so that it can inhibit and reduce oxidative stress and related damage. Quercetin also has a variety of biological activities， such as antioxidant， antiviral， anti-tumor and so on. In addition， quercetin shows the potential to treat and prevent a variety of diseases， such as cancer， osteoporosis， asthma， Alzheimer's disease， diabetes and skin diseases. Molecularly imprinted polymers（MIPs） are chemically synthesized receptors with pre-designed binding sites and rigidity to target molecules and have important applications in many fields， such as chemical sensing， separation， catalysis and disease diagnosis. Boric acid is an important functional monomer which can reversibly bind nucleosides， sugars， polysaccharides and glycoproteins to cis-diol compounds in covalent imprinting. In recent years， boric acid functional materials have attracted more and more attention. Considering the importance of selectivity and sensitivity to the efficiency of detection methods， a new imprinting strategy， called boric acid affinity surface oriented imprinting， was proposed by combining the covalent bin-ding of boric acid affinity with molecular imprinting technique. It is used to prepare high performance molecularly imprinted materials. This directed imprinting strategy is based on the interaction between the functional solid matrix and the template. In the process of template immobilization， the covalent interaction（boric acid affinity） is more stable than the non-covalent interaction， and the imprinting process can produce a more uniform distribution of binding sites. In addition， the interaction between boric acid ligands and cis-diol molecules is easily destroyed by acidic solution， which is beneficial to the removal of templates. Therefore， combined with the surface imprinting technique， the surface imprinting guided by boric acid affinity can almost completely remove the template molecules and provide more accessible binding sites for the target molecules. Using boric acid functionalized magnetic carbon nanotubes as reaction matrix， quercetin magnetic MIPs was prepared by a simple and green boronate affinity surface oriented imprinting method. It was also applied to the specific recognition of quercetin in ginkgo biloba extract powder. Transmission electron microscope， X-ray photoelectron spectroscopy， X-ray diffraction and vibrating sample magnetometer tests showed that the prepared MIPs had good morphology and crystal structure. A series of adsorption experiments showed that the MIPs had an ideal adsorption capacity（4.57 μg/mg）， a high selectivity（IF=8.44）and regeneration ability for quercetin. The adsorption experiments of the actual samples of Ginkgo biloba extract showed that the established method could achieve the expected detection effect of quercetin and could be used as an effective tool for specific identification of quercetin in traditional Chinese medicine.



Construction of a Label-free Electrochemical Ochratoxin Aptasensor Based on Pt Nanoparticles@ metal-organic Framework Nanomimetic Enzyme

LI Mei, XIA Xiaojuan, CHEN Zhixiong, YANG Meng, LI Ziying, YANG Tong, MENG Shuang, YANG Yunhui, HU Rong

2021, 42(12):  3615-3623.  doi:10.7503/cjcu20210409

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Pt NPs@Mn-MOF nanocomposite material with peroxidase-like properties was used as electrode substrate， and a label-free electrochemical aptasensor was constructed by screen printing electrode for the detection of ochratoxin（OTA）. Utilizing the nanomimetic enzyme characteristics of Pt NPs@Mn-MOF， Pt NPs@Mn-MOF was used as an electrode substrate to capture OTA aptamer chain and catalyze the reduction of H₂O₂ to generate current response signal. The introduction of OTA can obdurate the catalytic active sites of the nanomimetic enzyme， which leads to the decrease of current signal. In the range of 0.01—300 ng/mL， the current response value decreases gradually with the increase of OTA concentration. The current response signal was detected by the chronoamperometry， so the quantitative detection of OTA was realized indirectly. In addition， the aptasensor can be detected through a small U-disk type electrochemical workstation， which can be connected to a computer or a mobile phone for real-time detection. It has high detection sensitivity and good reproducibility， and the detection limit is as low as 3.33 pg/mL（S/N=3）. The constructed aptasensor can be used for OTA detection in real corn samples， and shows potential application in mycotoxin detection.



Evaluation of Quantitative Phosphoproteomic Performance of Sequential Enrichment of Metal Oxide Affinity Chromatography for Phosphopeptides Using TMT 10-plex Isobaric Labeling

ZHAO Huanhuan, LI Cunyu, JIN Hong

2021, 42(12):  3624-3631.  doi:10.7503/cjcu20210406

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A rapid， simple and high-flux strategy for quantitative phosphorylated proteomics was explored and developed， which was a kind of sequential enrichment method for complementary phosphopeptides labeled with Tandem mass tag（TMT） reagents. We cultured HepG2 cells treated with alkannin for 24 h and normal HepG2 cells for phosphorylation modification analysis. All the proteins were digested fully with Trypsin and labeled with TMT reagents， followed by desalting and vacuum drying. We implemented a SMOAC（Sequential enrichment of metal oxide affinity chromatography） strategy. We used firstly titanium dioxide（TiO₂） chromatography for phosphopeptides enrichment. Flow-through and wash fractions from TiO₂ were pooled and enriched secondly by ferrie nitrilotriacetate（Fe-NTA） chromatography. The platform equipped with EASY-nLC1200 and Orbitrap Exploris 480 mass spectrometry was applied to acquiring the phosphopeptides data of the HepG2 cells. We implemented two parallel sets of SMOAC strategy for 600 μg hybrid peptides labeled with TMT reagents. One of the sets， we pooled two kinds of eluate from SMOAC strategy for mass spectrometry analysis. Another of the sets， we analyzed the two kinds of eluate with mass spectrometry， respectively. Altogether we identified 4263 proteins and 16335 phosphopeptides， including 13347 phosphopeptides and 13851 phosphosites of 3848 proteins common to all channels from pooled eluate of SMOAC strategy. The specificity of the enrichment strategy was larger than 97% and 90% of the phosphoproteins identified were quantified. The study reveals SMOAC effectively improves the identification efficiency of phosphorylated peptides and also can quantify phosphorylation protein of a small amount of samples， combining with TMT reagents.



Characteristic Analysis of C₁—C₃n-Aldehydes and n-Alcohols in Proton Transfer Reaction Time-of-flight Mass Spectrometry

WANG Ruxin, ZHAO Zhongjun, HE Feiyao, YUE Hanlu, DENG Fulong, LI Hong, LI Wenwen, DUAN Yixiang

2021, 42(12):  3632-3640.  doi:10.7503/cjcu20210318

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Proton transfer reaction time-of-flight mass spectrometer（PTR-TOF-MS） is a kind of soft chemical ionization mass spectrometry instrument， which can realize real-time online detection of trace volatile organic compounds. The E/N value（E： electric field intensity， N： gas molecule number density） is an important parameter in the proton transfer reaction， which will affect the type and content of product ions. Herein， the effects of different E/N values on the types and relative strengths of C₁—C₃n-aldehydes and n-alcohol product ions were systematically investigated， and the proton transfer reaction characteristics of C₁—C₃ n-aldehydes and n-alcohols as well as the formation pathways of fragment ions were studied. The results show that low molecular weight n-alcohols（methanol， ethanol and propanol） tend to form protonated polymers ［nMH］⁺ and their dehydrated ions ［nMH-H₂O］⁺， and as the E/N value increases， n-alcohols will produce more fragments and polymer ions. Low molecular weight n-aldehydes（formaldehyde， acetaldehyde and propanal） mainly produce protonated products ［MH］⁺ and monohydrate protonated products ［M·H₃O］⁺. High E/N value（>125 Td） will inhibit the protonation of formaldehyde and the formation of its adducts. Acetaldehyde is more inclined to form water adducts， and the change trend of ［CH₃CHOH］⁺ and ［CH₃CHOH·H₂O］⁺ is opposite with the increase of E/N value. In addition， propanal will produce a series of polymers（［C₂H₅CHOH·C₂H₅］⁺， ［C₂H₅CHOH·C₂H₅CHO］⁺） at higher E/N values. In this paper， the best analytical E/N values and characteristic fragment ions of C₁—C₃n-aldehydes and n-alcohols were obtained， which is expected to provide an important basis for the qualitative and quantitative analysis of low molecular weight aldehydes and alcohols.



Organic Chemistry

Synthesis of （E）-α-Hydroxyethyl-α，β-unsaturated Aldehydes with Tetrahydrofuran as Carbonyl Source

PU Weiwen, SHI Yongsen, LIU Jianfeng, KE Dehong, WU Xiaolan, XU Sheng

2021, 42(12):  3641-3650.  doi:10.7503/cjcu20210486

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In this paper， THF was used as carbonyl source and tert-butyl hydroperoxide（TBHP） was used as oxidant to oxidize THF to 2-hydroxytetrahydrofuran， and then isomerization to 4-hydroxybutyraldehyde by ring-opening reaction， then it reacted with ethanolamine under acid catalysis to form imine intermediate（M）. On the other hand， benzaldehyde was obtained from benzyl alcohol by copper catalyzed oxidation reaction， and then reacted with M to obtain stereospecific（E）-α-hydroxyethyl-α，β-unsaturated aldehydes， which was further derivatized to obtain the α-functionalized α，β-unsaturated aldehydes. The configuration of the product was confirmed by COSY（homonuclear chemical shift correlation spectroscopy）. Our method has the advantages of low cost and simple synthesis process.



Chiroptical Molecular Switches Based on Reversible Electroacid/Electrobase

GONG Yiran, CHEN Changbing, MAO Qiannan, MA Dongliang, LIU Guoquan, YANG Guojian, ZHANG Yumo

2021, 42(12):  3651-3656.  doi:10.7503/cjcu20210478

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Chiroptical molecular switches have been intensively investigated in recent years due to their broad applications in the fields of optical storage， optical communication， three-dimensional imaging， etc. However， some drawbacks， such as few materials， poor optical tunability and poor stability of current chiroptical molecular switches， hinder their applications to construct a chiroptical switching device with high optical tunability and ideal stability. Thus， how to develop a chiroptical switching system with promising performances is still a serious challenge for the researchers. Herein， based on the reversible ‘electroacid/electrobase’ theory， we designed and synthesized a novel acid-responsive chiroptical molecular switch by introducing a chiral binaphthyl functional group into the acid-sensitive rhodamine structure. A novel chiroptical switching system has been successfully developed by the acid-responsive chiroptical molecular switches combining with electroacid materials， as its chiroptical property can be switched by the electric field reversibly. The results show that the color， fluorescence and circular dichroic（CD） signals of this new material could be reversibly regulated under the control of a suitable electric field. In conclusion， this method provides a brand new idea of constructing new chiroptical molecular switching systems， and it will be beneficial for expending the properties and applications of chiroptical molecular switching materials in the future.



Antifungal Mechanism of Fubaiju Essential Oil According to Labeling Method

FU Jun, WU Meichan, WANG Shuzhen, SHAO Xiuli, HE Feng

2021, 42(12):  3657-3663.  doi:10.7503/cjcu20210462

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Fubaiju essential oil was prepared by organic solvent extraction and steam distillation method. The cells， cell membrane， nucleic acid， mitochondrion and circular plasmid pCAMBIA1303 of S. cerevisiae were labeled with Jianna green， 1，1'-dioctadecyl-3，3，3'，3'-tetramethylindocarbocyanine perchlorate， propidium iodide， rhodamine 123 and ethidium bromide respectively to investigate antifungal mechanism of Fubaijuessential oil. According to the results of fluorescence microscope， Fubaiju essential oil showed antifungal activity against S. cerevisiae. Fubaiju essential oil could not only destroy the cell membrane， make the cell contents leak out， but also penetrate the cell membrane， destroy the mitochondrial membrane and DNA， and eventually lead to cell death.



Physical Chemistry

Rapid and Accurate Calculation of the Three⁃body Interaction Strength in the Hydrogen⁃bonded Complexes of Alcohols or Deoxyribose with Water

LI Xiaolei, SUN Yunjiao, TANG Ying, WANG Changsheng

2021, 42(12):  3664-3671.  doi:10.7503/cjcu20210564

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It is important to accurately and rapidly calculate the three-body interaction energies in the hydrogen-bonded complexes of alcohols or deoxyribose with water， especially for simulating the structures and functions of proteins and DNA in aqueous environments. Based on the understanding of the essence of many-body polarization effects， we estimated the three-body interaction energies of the hydrogen-bonded complexes composed of alcohols or deoxyribose with water via the polarizable dipole-dipole interaction model through regarding the polar chemical bonds O—H and C—O as bond-dipoles. The corresponding parameters were obtained by fitting to the three-body interaction energy curves with respect to the intermolecular distance of a methanol-water complex. The accuracy of our model and the transferability of parameters were validated through calculating the three-body interaction energies of the complexes of methanol， ethanol or deoxyribose with water. The calculated results demonstrated that our polarizable dipole-dipole interaction model and the parameters determined in this work can accurately estimate the three-body interaction energies of different hydrogen-bonded complexes， and the accuracy of our model is comparable with that of MP2 method.



Group Contribution Method for Infinite Dilution Molar Conductivity of Unconventional Ions in Water

WAN Ren, SONG Fan, PENG Changjun, LIU Honglai

2021, 42(12):  3672-3679.  doi:10.7503/cjcu20210540

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Unconventional ions refer to ions that have been appear with the continuous creation of ionic liquids（ILs）， and their most attractive feature is that they can be designed. When ILs are in an infinite dilution state， the most important transfer property is the infinite dilution molar conductivity（{\lambda }_{\mathrm{B}}^{\mathrm{\infty }}）of a single ion， which reflects the solvation of the ion and is an important link between different transfer properties. The group contribution method（GCM）was established to predict the infinite dilution molar conductivity model（{\lambda }_{\mathrm{B}}^{\mathrm{\infty }}-GCM） of imidazole cations and quaternary ammonium cations， and obtain the contributions of the imidazole central ion［Im］， alkylammonium［N］， methyl［—CH₃］， methyl［—CH₂—］， ring hydrogen［ring-H］， ether group ［—O—］， hydroxyl group［—OH］ and other groups to the infinite dilution molar conductivity. The established {\lambda }_{\mathrm{B}}^{\mathrm{\infty }}-GCM can not only reflect the influence of different groups on the infinite dilution molar conductivity， but also reveal the relationship between the temperature and the infinite dilution molar conductivity. The results showed that more than 70% of data points predicted ln{\lambda }_{\mathrm{B}}^{\mathrm{\infty }} by GCM produced an absolute relative deviation of less than 2%， less than 1% of data points with an absolute relative deviation of more than 5% and the total average absolute relative deviation was 1.57%. Overall， {\lambda }_{\mathrm{B}}^{\mathrm{\infty }}-GCM is a simple and reliable method to predict the infinite dilution molar conductivity of unconventional cations.



Experimental and DFT Studies on the Adsorption of Cd（II） Ions from Aqueous Solutions by Nanofiber Modified Thiourea Groups

LI Min, ZHAO Chun, FENG Qinzhong, FENG Jian, MENG Xiaojing

2021, 42(12):  3680-3691.  doi:10.7503/cjcu20210534

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Cadmium is a highly toxic metal， and Cd（II） ions is a great threat to the ecological environment and human body. Herein， a new nanofiber modified thiourea groups was prepared using polyacrylonitrile （PAN） as the raw materials based on electrospinning and chemical grafting， which was used as an efficient adsorbent to remove Cd（II） ions from aqueous solutions. Several characterized techniques， including Fourier transform infrared spectroscopy（FTIR）， scanning electron microscopy（SEM）， thermogravimetric analysis （TGA） and X-ray photoelectron spectroscopy（XPS） and density functional theory（DFT） theoretical calculations， were introduced to reveal the adsorption mechanism of FGTG（fiber modified by thiourea group） towards Cd（II） ions. The adsorption behavior of Cd（II） ions on the FGTG was investigated through batch and column experiments. The results show that the maximum uptake of Cd（II） ions on the FGTG was 349.46 mg/g. The adsorption equilibrium was reached within 90 min and the adsorption isotherms fitted well with the Langmuir isotherm， and the obtained kinetic data support a pseudo-second order adsorption process. The adsorption mechanism of Cd（II） ions on the FGTG is the surface coordination complexation， and it is an important way to improve the adsorption capa? city of Cd（II） ions to enhance the content of thiourea groups in the adsorbent. Moreover， obvious change on the dynamic adsorption uptake of Cd（II） ions was not been found even after six cycles. An adsorbent on Cd（II） ions with low flow resistance was fabricated in this study and the adsorption mechanism was revealed by a series of characterized techniques and DFT.



Co-catalytic Effect of Ni₂P on Photocatalytic Formic Acid Dehydrogenation over Different Semiconductors

XIAO Zhaozhong, MA Zhi, PIAO Lingyu

2021, 42(12):  3692-3700.  doi:10.7503/cjcu20210508

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The co-catalytic effect of Ni₂P in the field of photocatalytic formic acid dehydrogenation on different photocatalysts（TiO₂， CdS and C₃N₄） was studied. Ni₂P as a cocatalyst combined with the three semiconductors showed good activity for hydrogen production from formic acid decomposition. The optimal H₂ evolution rate reaches 41.69， 22.45 and 47.67 μmol·mg^-1·h^-1 under the optimal HCOOH concentration over Ni₂P/TiO₂， Ni₂P/CdS and Ni₂P/C₃N₄ photocatalyst， respectively， which are 3.8， 10 and 210 times greater than those of pure TiO₂， CdS and C₃N₄. The result indicates that Ni₂P has universality in photocatalytic decomposition of formic acid for hydrogen production. Finally， the mechanism of photocatalytic hydrogen production was proposed. The introduction of Ni₂P significantly accelerates photogenerated electrons transfer from semiconductor to Ni₂P and the separation of photogenerated electrons. At the same time， Ni₂P promotes the formation of active species ·OH and enhances H₂ evolution efficiency. These research results show that nickel phosphide has high hydrogen production activity. It has a good application prospects for constructing an efficient photoca? talytic formic acid dehydrogenation system.



Efficient Synthesis of Dimethyl Carbonate via Transesterification of Methanol and Ethylene Carbonate Catalyzed by Poly（ionic liquid）s

WANG Man, WANG Xin, ZHOU Jing, GAO Guohua

2021, 42(12):  3701-3708.  doi:10.7503/cjcu20210498

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A series of poly（ionic liquid）s containing carboxylate anions was synthesized by free radical copolymerization of N-vinylimidazolium ionic liquids， sodium acrylate and crosslinker divinylbenzene（DVB） or 1，8-triethylene glycoldiyl-3，3′-divinylimidazolium bromide｛［（EG）₃-DVIm］Br₂｝. These poly（ionic liquid）s were characterized by nuclear magnetic resonance（NMR） spectroscopy， Fourier transform infrared spectro?scopy（FTIR） and thermogravimetric analysis（TGA）. The swelling properties of poly（ionic liquid）s in methanol-EC mixed solvents could be regulated by cross-linking agents and 3-alkyl-substituents on imidazolium. These poly（ionic liquid）s were used to catalyze the transesterification of methanol and ethylene carbonate（EC） to synthesize dimethyl carbonate（DMC）. The catalytic activity of poly（ionic liquid）s increased with the increase of swelling ratio. And poly［VOIm-AA-DVIm］， which had the highest swelling ability（Q=25.9） in the mixed solvent of methanol and EC， had the highest catalytic activity. The effects of temperature， reaction time， amount of catalyst and molar ratio of methanol to EC on the transesterification process over the poly［VOIm-AA-DVIm］ were investigated and discussed， respectively. Under the optimized reaction conditions［120 ℃， 6 h， 1.0% catalyst（molar fraction， based on carboxylate）， n（methanol）n（/EC）=10∶1］， the yield of DMC was 76.6% and the selectivity was 90.1%. The catalytic activity was comparable to that of the homogeneous catalyst 1-butyl-3-methylimidazole acetate（［BMIm］OAc）.



Group Additivity Theoretical Model for the Prediction of Dielectric Strengths of the Alternative Gases to SF₆

HOU Hua, WANG Baoshan

2021, 42(12):  3709-3715.  doi:10.7503/cjcu20210495

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Dielectric strength is one of the most parameters for the design and discovery of novel eco-friendly replacement gases for SF₆. Various structure-activity relationship models had been widely used to predict the dielectric strength on the basis of the quantum chemistry calculated descriptors， which are computationally demanding and usually involve significant uncertainties and incapability of treating some specific compounds. In order to predict the dielectric strength of a gas straightforwardly， group additivity method was proposed in this work. Within the first-order approximation， the direct summation of the optimized individual contributions of the functional groups gives the overall dielectric strength. In comparison with a total of 65 insulating gases， the agreement between group additivity and experimental data is excellent. The mean absolute and relative deviations are 0.0656 and 6.28%， respectively. The correlation coefficient between theory and experiment is 0.9879， which are all superior to the structure-activity relationship models. The result reveals that inducing the unsaturated group or cyclic moiety and substituting the isolated CH_x and CF by CF₃， OCF₃， and SCF₃ is efficient to improve the dielectric strength.



Rapid Detection of Banned Dyes in Textiles Based on Surface-enhanced Raman Spectroscopy

PAN Jing, XU Minmin, YUAN Yaxian, YAO Jianlin

2021, 42(12):  3716-3721.  doi:10.7503/cjcu20210490

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Dye is one of the most important compounds. The textile industry consumes more than half of its total production each year， so dyes have a critical impact on the safety of textiles. The improvement of lifestyle has prompted people to pursue more safety of clothing. In addition， the frequent safety accidents of textile dyes have made relevant institutions focus on the development of more effective detection technology. Most of the banned dyes have carcinogenicity， teratogenicity， sensitization and other hazards to the human body. Moreover， many harmful dyes can exist in light， solvents and most chemical substances for a long-time， and it has difficult to degrade， causing harm to the environments. The development of rapid and sensitive technique is highly desired for the detection of banned dyes. Herein， based on surface-enhanced Raman spectroscopy（SERS）， a rapid qualitative method for dyes in textiles was established. SERS technology exhibits high detection sensitivity and fast detection speed for more accurate qualitative detection of dyes. Two kinds of dyes （basic red 9 and disperse yellow 23）， which are prohibited in the national standards， were employed as the model probe molecules. Silver nanoparticles were fabricated by one-step method， and the substrate optimization experiment was carried out. Combined with SERS technology， the rapid identification of dyes in textiles was achieved. It was revealed that the limit of detection（LOD） of these two dyes in textiles was about 0.16 and 0.24 mg/kg for basic red 9 and disperse yellow 23， respectively. The LOD was one order of magnitude higher than the national standard. It demonstrated that the SERS based approach could be developed as promising technique for direct and rapid evaluation of textile safety.



Photocatalytic Reduction Performance of Z-scheme Two-dimensional BCN/Sn₃O₄ Composite Materials

WANG Yishu, LI Xue, YAN Li, XU Hongyun, ZHU Yuxin, SONG Yanhua, CUI Yanjuan

2021, 42(12):  3722-3730.  doi:10.7503/cjcu20210470

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The research on the Z-Scheme heterostructure composition of carbon nitride-based polymer mate- rial is an important strategy to improve its photocatalytic performance. Two-dimensional boron-doped carbon nitride（BCN） and Tin tetroxide（Sn₃O₄） semiconductor materials were prepared by direct thermal polymerization and hydrothermal synthesis， respectively. And BCN/Sn₃O₄ composites were constructed by ultrasonic composite and calcined composite methods. The prepared samples were characterized and analyzed by means of X-ray diffraction（XRD）， ultraviolet-visible diffuse reflectance（UV-Vis）， transmission electron microscopy（TEM）. The microstructure and photoelectric properties of the catalyst prepared from different methods were discussed. At the same time， the photocatalytic performance of the catalysts was investigated by using visible light photolysis of water to produce hydrogen and activated oxygen to produce hydrogen peroxide. The results showed that BCN and Sn₃O₄ can form a two-dimensional surface-to-surface composite structure， and compared to the ultrasonic composite method， the direct calcination method is more conducive for the formation of an effective interface， causing the charge transfer from Sn₃O₄ to BCN between the interface and enhancing the surface charge density of BCN. This composite material had much optimized photoelectric response and photocatalytic reduction activity. Among them， the sample BCN/Sn₃O₄-3C（mass ratio of Sn₃O₄/BCN=3%） prepared by calcination method showed significantly enhanced photolysis of water to produce hydrogen and activated oxygen to produce hydrogen peroxide. This work provides a new research idea for the construction of carbon nitride-based Z-scheme photocatalytic systems.



Preparation of CoCr_x/SAPO-34 Catalyst and Its Catalytic Combustion Performance for 1，2-Dichloroethane

WU Shuaini, ZHU Pengfei, SHI Huaiqi, LI Na, HU Zhaoxia, CHEN Shouwen

2021, 42(12):  3731-3737.  doi:10.7503/cjcu20210469

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Catalytic combustion is one of the most efficient and economical methods for the treatment of chlorinated volatile organic compounds（CVOCs）. For the exploration of high-efficient catalyst， SAPO-34 type molecular sieve was synthesized by hydrothermal method using triethylamine and tetraethylammonium hydroxide as composite templates， and subsequently used as support to prepare a series of CoCr_x/SAPO-34 catalysts （x=0.05—0.25） by rotary steam impregnation method. Structure and surface acidity of these catalysts were investigated， and their catalytic combustion performance was evaluated with 1，2-dichloroethane（1，2-DCE） as the target pollutant. The results showed that the CoCr_0.06/SAPO-34 catalyst with the loading of 20%（mass fraction） Co₃O₄ and the Cr doping ratio of 0.06 exhibited excellent catalytic activity for 1，2-DCE（T₉₀=290 ℃）. At 290 ℃， the catalytic conversion of 1，2-DCE over CoCr_0.06/SAPO-34 can be maintained beyond 80% for 45 h， showing excellent stability and resistance to chlorine poisoning.



Polymer Chemistry

Regulation of Rheological Behavior of Polyvinyl Alcohol Aqueous Solution by One-dimensional Particles

NI Qingsheng, DU Miao, SHAN Guorong, SONG Yihu, WU Ziliang, ZHENG Qiang

2021, 42(12):  3738-3745.  doi:10.7503/cjcu20210597

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In this paper， one-dimensional particles were added into polyvinyl alcohol（PVA） aqueous solution. The effects of oxygen-containing functional group content（hydroxyl value） on the surface of carbon particles， aspect ratio（L/D）， temperature and PVA bulk solution concentration on the rheological behavior of the composite solution were investigated. The results show that carbon nanotubes（CNTs） and carbon nanofibers（CF） can regulate the rheological behavior of PVA aqueous solution by changing hydroxyl value and L/D. The viscosity（η） of the composite solutions first increases， then decreases， and then continues to increase with the amount of CNTs（{\phi }_{\mathrm{C}\mathrm{N}\mathrm{T}\mathrm{s}}）， showing an “N” shape change trend. There are two transition points， i.e. {\phi }_{\mathrm{1}} and {\phi }_{\mathrm{2}}. CNTs mainly play a role of physical crosslinking point at {\phi }_{\mathrm{1}}， and the η increases； while CNTs destroy the intermolecular hydrogen bond interaction of PVA chains most seriously at {\phi }_{\mathrm{2}}， leading to a lower η than that of pure PVA solution. With the increase of hydroxyl value， the interactions between CNTs and PVA chains are strengthened， giving rise to the decrease of both {\phi }_{\mathrm{1}} and {\phi }_{\mathrm{2}}. Furthermore， η corresponding to {\phi }_{\mathrm{2}} decreases. This indicates the viscosity reduction effect is strengthened by the high hydroxyl value of CNTs. With the addition of CNTs， the hydration number of the composite solution decreases， implying that more hydroxyl group of PVA chains form hydrogen bond interaction with CNTs. The CNTs composite solution with high hydroxyl value has lower hydration number than that with low hydroxyl value. The viscous activation energy of the composite solution increases with {\phi }_{\mathrm{C}\mathrm{N}\mathrm{T}\mathrm{s}}. CNTs have similar regulatory effects on η of PVA solutions with different concentrations， but the regulatory range is different. The viscosity regulation of PVA aqueous solution by CNTs with the same hydroxyl value and different L/D also show an “N” shape curve， but short CNTs composite solution with small L/D have large {\phi }_{\mathrm{1}} and {\phi }_{\mathrm{2}}. While the composite solutions containing CF with similar L/D but larger diameter show lower {\phi }_{\mathrm{1}} and {\phi }_{\mathrm{2}}.



Preparation and Properties Characterization of Polysiloxane Skin Tissue Adhesive

CHEN Binggang, LIU Sanrong, YU Xifei, JIANG Zijiang

2021, 42(12):  3746-3756.  doi:10.7503/cjcu20210590

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Skin is inevitably injured as the outermost organ of human body in daily life. Suture is the main methods to deal with the open skin wounds. However， even if suture can effectively close the open wounds， it may cause some defects such as secondary damage and scars. It is ideal to develop the tissue adhesive with good performance to replace the suture. Based on the analysis of properties requirements of skin tissue adhesive， a polysiloxane skin tissue adhesive was designed and synthesized which is consisted of prepolymer poly（dimethyl siloxane）_n-co-poly（propoxybenzaldehyde methyl siloxane）_m（PDMS_n-PBAMS_m）， crosslinker poly（hydromethyl siloxame）PHMS and Karstedt’s catalyst. Among them， the side groups of prepolymer with functional modification can covalently interact with skin， prepolymer and PHMS can occur rapid in situ curing reaction to achieve adhesion on skin. The results indicate that polysiloxane tissue adhesive has compatible mechanical properties with skin through adjusting the degree of polymerization（DP） of prepolymer， modified proportion of functional group and content of PHMS. The adhesion tests indicate that the polysiloxane has good adhesive property for hogskin and the maximum shear adhesive strength is 77.6 kPa. In addition， prepolymer and PHMS complete in situ curing process in about 100 s at room temperature. Polysiloxane adhesvie can meet the property requirements as a good skin tissue adhesive and has a good application prospect in regenerative medicine.



Preparation and Properties of 3-Methylcatechol/Furfurylamine Based Polybenzoxazine

CHEN Chen, LU Xin, ZHAO Yudi, WANG Litong, XIN Zhong

2021, 42(12):  3757-3764.  doi:10.7503/cjcu20210439

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3-Methylcatechol/furfurylamine benzoxazine（M-f） containing phenolic hydroxyl group was synthesized to develop a benzoxazine that could be cured at relatively low temperature. The peak exothermic temperature（T_p） of M-f measured by differential scanning calorimetry（DSC） is 172 ℃， while the T_p of meta-cresol/furfurylamine benzoxazine（MC-f） is 244 ℃， indicating that the introduction of phenolic hydroxyl groups is beneficial to reduce the ring-opening curing temperature of benzoxazine. The curing kinetics of the two benzoxazine monomers were studied by non-isothermal DSC methods. The calculation results of Kissinger method and Ozawa method both indicated that the apparent activation energy of M-f was lower than that of MC-f. In addition， the adhesion performance of polybenzoxazine to metal substrate was explored by lap shear strength testing. The testing results demonstrated that the lap shear strengths of the M-f polymer to the aluminum and mild steel substrates reached 2.53 MPa and 3.09 MPa， respectively， which were higher than those of the MC-f polymer.



Synthesis and Optical Properties of Polycarbonates Copolymerized with Bisphenol Fluorene Moiety

DU Xinyao, WANG Wei, LIN Yu, WU Guozhang

2021, 42(12):  3765-3773.  doi:10.7503/cjcu20210382

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To reduce the birefringence of bisphenol A polycarbonate（BPA-PC）， we intended to copolymerize bisphenol fluorene（BPEF） with BPA to prepare a copolycarbonate with intrinsic birefringence close to 0. We observed that catalysts with a large basic pK_a value can reduce the difference in reactive activity between BPA and BPEF， thus increasing the molecular weight of copolycarbonates. When the polycondensation temperature is 265 ℃ and time is 40 min， the weight-average molecular weight of the synthesized PC with a feed molar ratio of BPEF/BPA of 40/60 reaches 39800. ¹H NMR and ¹³C NMR analysis testify that all products are random copolymers. Increasing the content of BPEF leads to a high refractive index and a low birefringence value. When the BPEF molar fraction is 87%， the intrinsic birefringence is approximately 0.0028， which is very close to zero birefringence.



Materials Chemistry

Fast Synthesis of Highly Luminescent Two-dimensional Tin-halide Perovskites by Anti-solvent Method

LIU Yao, DENG Zhengtao

2021, 42(12):  3774-3782.  doi:10.7503/cjcu20210358

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In recent years， lead halide perovskites have attracted extensive attention due to their remarkable optoelectronic properties. However， the toxicity of lead in materials has greatly hindered their large-scale commercial applications. Therefore， it is very important to find lead-free halide perovskite materials with similar photoelectric properties as lead halide perovskite materials. Among the lead-free halide perovskites， tin-halide perovskite is considered as one of the best substitutes for lead based perovskite materials. Herein， a series of novel two-dimensional（2D） （RNH₃）₂SnX₄（R is alkyl chain， X=Br^-， I^-） perovskite materials was synthesized by a simple antisolvent method， which have excellent fluorescence emission properties with photoluminescence quantum yield（PLQY） up to 98%. It was found that the prepared materials are more stable than 3D ASnX₃-type［A=Cs⁺， methylammonium（MA⁺）， formamidinium（FA⁺）］ ones. This work lays a foundation for the industrial application of metal halide perovskite materials in solid-state lighting devices and display devices.