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10 November 2023, Volume 44 Issue 11
Cover and Content of Chemical Journal of Chinese Universities Vol.44 No.11(2023)
2023, 44(11):  1-6. 
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Articles: Inorganic Chemistry
Structural Transformation and Luminescence Properties of Terbium-sulfonylcalix[4]arene Mononuclear Complexes
MAO Dongao, XU Linmeng, BI Yanfeng
2023, 44(11):  20230107.  doi:10.7503/cjcu20230107
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A mononuclear terbium coordination compound(Tb1-A) was prepared from t-tert-butyl-sulfonylcalixarene(H4TC4A-SO2) and Tb(CH3COO)3. Calixarene can effectively sensitize terbium ions, enabling luminescence of Tb1-A in both solid state and methanol solution. It was found that 1,10-phenanthroline(phen) could influence the luminescence of Tb1-A by two interaction modes in fluorescence titration. Two different contacting modes between phen and Tb1-A were also determined by the single crystal structural characterization of two mononuclear compounds(Tb1-B and Tb1-C), one of which was the coordination between phen and Tb ions, the other was the host-guest interaction between phen and calixarene. Combined with the results of theoretical calculation, it was also found that the host-guest interaction between guest molecules and calixarene was the main factor that caused the fluorescence quenching.

Analytical Chemistry
Direct Evaluation of Single-strand Break Repair Capacity of Cells Using a Pyrene Excimer-based Hairpin Probe
LI Yin, LIU Jinsong, WANG Yu, QI Tingting, MENG Leyuan, ZHANG Jing, LYU Dongmei, JIAO Huping
2023, 44(11):  20230288.  doi:10.7503/cjcu20230288
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A novel pyrene excimer-based hairpin probe with a nick at the stem was developed to directly evaluate the single-strand break repair(SSBR) ability. In the existence of appropriate activity of DNA repair-associated enzymes(DREs), the oligonucleotide probe could prevent the digestion of Bst DNA polymerase and keep the long-wavelength excimer signal. However, in the absence of DREs, the nicked probe could be digested by Bst DNA polymerase, bringing about a “turn-off” monomer fluorescence signal. Therefore, the fluorescence changes of the probe could be used to directly evaluate the SSBR capability. After feasibility verification and a series of conditions optimization, the assessment of SSBR capacity by nucleoprotein extracted from different cells was investigated and the results showed that, compared to the primary cell, the tumor cell lines do not have the ability of SSBR. We also explored the deficiency of tumor cells SSBR by compensation with extra SSBR key enzymes and the results indicated that something might inhibit the SSBR in tumor cell lines. Furthermore, the reporter system could detect SSBR of 500 cells and was successfully applied to anti-aging drug screening. The advantages of this method include simple procedure, less time, and good repeatability, and this method can be used for the rapid detection of SSBR capacity of different cells.

Vinyl Sulfone Functionalized Magnetic Nanoparticles and Its Application in Palmitoylated Peptides Enrichment
ZHENG Haijiao, XU Wenhui, JIA Qiong
2023, 44(11):  20230239.  doi:10.7503/cjcu20230239
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Vinyl sulfone modified magnetic nanoparticles(denoted as MagBVP) were synthesized and used as the magnetic carrier of magnetic solid phase extraction(MSPE) platform, combined with MALDI-TOF MS or LC-MS/MS. The MagBVP was characterized by means of vibrating sample magnetometer, field emission scanning electron microscopy, infrared spectroscopy, zeta potential measurement and X-ray diffraction. The synthesized palmitoylated palmitoyl-coA was selected as the modeling palmitoylated peptide sample. Under the optimal conditions, the MSPE-MS platform could achieve high selectivity(BSA tryptic digests/palmitoylated peptide molar ratio of 2000∶1) and sensitivity(the detection limit was determined to be as low as 1.0 fmol/μL) for palmitoylated peptide. Finally, the method was applied to the determination of palmitoylated peptides in cell lysates samples. These results showed that the magnetic material modified by vinyl sulfone had a high selectivity for palmitoylomics.

Organic Chemistry
Mechanofluorochromic and Inkless Writing Test of Pyridine-based Difluoroboron Complex with Triphenylamine Moiety
WANG Fupeng, TIAN Jiazhuang, YANG Yanhua, GAO Shulin
2023, 44(11):  20230326.  doi:10.7503/cjcu20230326
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In order to explore the photophysical property and practical application of difluoroboron complex, a D-π-A type difluoroboron complex 4'-(1,1-difluoro-1H-1λ4,9λ4-pyrido[1,2-c][1,3,5,2] oxadiazaborinin-3-yl)- NN-diphenyl-[1,1'-biphenyl]-4-amine(Py-TPA BF2) containing triphenylamine as electron donor and difluoroboron as electron acceptor was designed and synthesized. The photophysical testing results indicated that the complex exhibited intramolecular charge transfer characteristic and aggregation-induced emission activity. Further studies showed that the fluorescence emission spectrum of the complex Py-TPA BF2 in solid state was red-shift from 530 nm to 550 nm under external stimulation, and the luminescence color changed from green to straw-yellow, and the color again returned to green after using dichloromethane vapor fuming. The X-ray diffraction testing results indicated that the phase transformation between the ordered crystalline phase and the disordered amorphous phase during grinding-fuming processes resulted in the reversible mechanofluorochromic performance of complex Py-TPA BF2. Furthermore, it could also be applied to data security protection for inkless writing, which would be conducive to the rational design of intelligent luminescent materials.

Design, Synthesis and Anti-fungal Activity of 1,2,4-Oxadiazole Derivatives Containing Diamide Moiety
WANG Feng, CHEN Yu, PEI Hongyan, LIU Dongdong, LUO Chunfeng, ZHANG Jing, ZHANG Lixin
2023, 44(11):  20230309.  doi:10.7503/cjcu20230309
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To search the novel and efficient antifungal lead compounds, twenty-seven 1,2,4-oxadiazole derivatives (compounds 4a─4c and 6a─6x) containing diamide moiety with novel chemical structures were designed and synthesized, which was based on the method of the splicing of bioactive substructures. The structures of target compounds were characterized by means of 1H NMR and HRMS spectra. The bioassay results showed that, at the concentration of 3.13 mg/L, the control effect of compounds 6f, 6i, 6m, 6n and 6q against Soybean rust(Phakopsorapachyrhiz) were 80%, 90%, 80%, 90% and 70%, respectively. The above activities were all better than Flufenoxadiazam(30%) and the control agent Difenoconazole(50%). Compound 6n also showed prominent antifungal activity against Corn rust(Pucciniasorghi), which control effect was 100% at the concentration of 1.56 mg/L. The molecular docking simulation revealed that compound 6n has various interactions with histone deacetylase 4(HDACs 4),which compound 6n interacts with PRO-298, LEU-299 and HIS-158 through hydrogen bond may be the important source why it showed prominent antifungal activity.

Design, Synthesis and Properties of High-contrast Cationic Mechanofluorochromic Materials
GENG Peng, XIANG Juanjuan, ZHANG Xinghong, YUAN Shuang, MAO Miaofu, LU Yunxiang, XIAO Shuzhang
2023, 44(11):  20230289.  doi:10.7503/cjcu20230289
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High-contrast organic mechanofluorochromic materials have potential applications in security ink and memory devices, but the mechanochromic materials with luminescence change over 100 nm are still limited. In this work, we designed a D-π-A organic molecule with large dipole moment NN-diphenyl-4-[2-(quinolin-2- yl)]aniliue hydrochloride(QV-TPA-HCl), and performed Polymorph for the design molecule. Polymorph indicated that it had the potential to form both monomer and π-π stacked cluster. Single crystal structure proved the formation of π cluster. Upon alternative grinding at 30 ℃ and 100 ℃, Near-infrared fluorescence(673 nm) and green luminescence(490 nm) could be obtained with luminescence difference 183 nm, due to the reversible conversion between the π cluster and monomer. Our investigation presents a rational strategy for designing high-contrast mechanochromic materials with significant luminescence change.

Preparation and Properties of a Flexible Photothermal Conversion Device of Azobenzene-based with Photoinduced Phase Transition Type
MIAO Guimei, CHEN Longxuan, GONG Piwen, HAN Jishu, ZHAO Ruiyang, LIU Fusheng
2023, 44(11):  20230256.  doi:10.7503/cjcu20230256
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A new kind of azobenzene derivative 1-[4-(allyloxy)phenyl]-2-(p-tolyl)diazenyl(AD-Azo) with room temperature photo-induced solid-liquid transition performance was designed and synthesized for solar thermal fuels(STFs) applications. At the same time, the energy storage density of the azobenzene derivative was greatly improved due to the latent heat of phase transition during solid-liquid conversion. Under light or heat induction, AD-Azo was combined with ordinary commercial fabric to prepare an environmentally friendly, ready-to-use flexible STF device. Moreover, there is a supramolecular interaction(hydrogen bond) between molecules in the fabric, which enhances the energy storage density and energy storage life. The total energy storage density of the STF device is as high as 199.12 J/g, and the energy storage half-life is 50 h. In addition, this flexible AD-Azo STF device possesses good flexibility, solvent stability and recyclability, which has potential application prospects in environment-friendly STFs.

Synthesis, Characterization, Biological Activity and Structure-activity Relationship of 6-N-heterocyclic Substituted Sanguinarine Derivatives
JIA Changqing, MA Rui, QIAN Xicheng, QIN Zhaohai, XU Houqiang
2023, 44(11):  20230231.  doi:10.7503/cjcu20230231
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A novel series of 6-N⁃heterocycle substituted sanguinarine derivatives was designed and synthesized by active group splicing with sanguinarine as lead. The structures of title compounds were confirmed by 1H NMR, 13C NMR, IR and HRMS. By using the mycelium growth rate method, title compounds were evaluated for antifungal activities in vitro and structure-activity relationships(SAR) were investigated. The preliminary antifungal activity test results indicate that compounds 3a⁃063a⁃073b⁃013c⁃07 and 3c⁃08 exhibited a relatively broad spectrum of fungicidal activity against ten tested pathogens at a concentration of 50 μg/mL, the inhibition rate against most of the tested pathogens is above 72%. In further precision virulence assay, some title compounds showed good antifungal activity. The median effective concentrations (EC50) of compound 3b⁃01 against Colletotrichum camalliae Massee and Thanatepephorus cucumeris were 8.52 and 9.77 μg/mL, respectively. The EC50 of compound 3c⁃08 against Colletotrichum camalliae Massee and Pestalotiopsis theae (Sawada) Steyaer were 9.17 and 8.83 μg/mL, respectively. Compound 3c⁃08 has the potential for application in the prevention and control of tea diseases. Compared with the lead compound sanguinarine hydrochloride, most of the title compounds showed better antifungal activity. The preliminary results of insecticidal activity showed that the insecticidal activity of these compounds against Myzus persicae was normal at a concentration of 400 μg/mL. In conclusion, these results laid a foundation for further development and utilization of sanguinarine derivatives.

Novel Black Electrochromic System Based on Urea-imidazolium Salts
HUANG Zhikang, WANG Tongtong, CHEN Yujing, HUANG Shiyu, WANG Jiajia, GUO Junnian, YU Yang
2023, 44(11):  20230226.  doi:10.7503/cjcu20230226
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Electrochromic(EC) materials have applications in smart windows, anti-glare rearview mirrors, reflective displays, etc. However, the performances of EC materials, such as their response speed and stability, are still not ideal. Thus, developing EC systems with high stability and fast optical switching speed is currently a serious challenge. In this paper, based on the proton-coupled electron transfer mechanism and the reversible “electroacid/base” method, we introduced imidazole-based ion-conducting structures with high ion conductivity and stability into urea-containing “electrochroacid”, and combined them with 2-anilino-6-dibutylamino-3-methylfluoran (ODB-2) to design and construct a novel black EC system. This newly developed system combines the advantages of ion- conducting materials and electrochromic materials. Under a suitable electric field, the color can be stably and reversibly switched between colorless and black. This paper provides a new approach for developing stable EC systems, which can help promote the application of EC materials.

Physical Chemistry
Construction and Electrochemical Properties of Si/rGO@CN as Anode Materials for High-performance Lithium-ion Batteries
ZHOU Hui, ZHU Shuaibo, WANG Jitong, QIAO Wenming, YU Zijian, ZHANG Yinxu
2023, 44(11):  20230354.  doi:10.7503/cjcu20230354
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In this paper, the self-charged graphene and the nano-silicon modified with positive charge were self- assembled by electrostatic self-assembly method, and then the dopamine bonding characteristics was used to nitrogen-doped carbon coating of the composite material to obtain Si/rGO@CN composites, and the effect of different thicknesses of nitrogen-doped carbon layers on the electrochemical performance of the composite materials was studied by changing the concentration and polymerization time of dopamine. The electrochemical results showed that when the content of nitrogen-doped carbon was 23.6%(mass fraction), the composite showed excellent electro- chemical performance. The capacity of the composite was 943.4 mA·h/g after 200 cycles at a current density of 0.2 A/g, and its capacity remained at 753.8 mA·h/g after 300 cycles in the long cycle performance test at a current density of 1.0 A/g. The uniform continuous coating of the nitrogen-doped carbon layer can not only avoid the direct contact between silicon and electrolyte, but also buffer the volume expansion generated by silicon nanomaterials during lithium intercalation and maintain the stability of the material structure. The presence of graphene improves the conductivity of composite materials.

Surface Adsorption of Water-alcohol Binary Solutions
YU Xianchao, QI Wenshuai, DENG Quanhua, HOU Wanguo
2023, 44(11):  20230316.  doi:10.7503/cjcu20230316
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Algebraic equations of the Gibbs surface excess(Γ2) and adsorption layer thickness(τ) were developed for binary liquid mixtures based on the surface aggregation adsorption(SAA) model and the Gibbs differential equation, which can predict the change of Γ2 and τ with the bulk composition(such as the molar fraction of component 2, x2,b) in the whole concentration range. The model equations were used to investigate the surface adsorption of water(1)-alcohol(2) binary solutions. The alcohols involved include methanol(MeOH), ethanol(EtOH), iso-propanol(iPrOH), n-propanol(nPrOH), and tert-butanol(tBuOH). It was found that their adsorption trend on the water surface increases in turn, consistent with the enhancement trend of their hydrophobicity. Their Γ2 and τ increase in turn in the low x2,b region, while decrease in turn in the high x2,b region, which arise from the differences in adsorption trend and molecular size between alcohols. In addition, for a given alcohol system, with an increase in x2,b from 0 to 1, its Γ2 initially sharply increases and then decreases, showing a maximum, but its τ exhibits a continuous reduction. This work provides a better understanding of the surface adsorption behavior of water-alcohol liquid mixtures.

Promotional Effect of Ni-Co/TiO2 Catalysts on CO2 Hydrogenation
WANG Zhaoyu, CHEN Yibin, CHENG Jintian, ZHANG Mingwen
2023, 44(11):  20230308.  doi:10.7503/cjcu20230308
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The Ni-Co/TiO2 catalysts were synthesized via an excess-solution impregnation method and fully characterized XRD, FESEM, EDS, TEM, XPS and N2 adsorption-desorption tests. In CO2 hydrogenation reaction for 3 h, Ni-Co/TiO2 catalyst exhibited a CH4 production of 84.4 μmol, which was enhanced by 46.3%, compared with Ni/TiO2. Results of CO2-TPD and H2-TPR demonstrated that the introduced Co can facilitate the adsorption and activation of CO2 molecules to contribute to the CO2 hydrogenation reaction. In the activity stability tests for 5 cycles, the yield of CH4 was reduced by 20.5% over Ni/TiO2, while that over Ni-Co/TiO2 was only by 10.9%, revealing that the introduced Co can also enhance the catalytic stability for the reaction. This study may provide some guidance for the design and synthesis of high-efficiency catalysts for CO2 hydrogenation.

Molecular Dynamics Simulation Study on High Temperature Oxidation Mechanism of n-Propylbenzene
ZHOU Zihao, WANG Sihao, HUANG Daichuan, LIU Bo, NING Hongbo
2023, 44(11):  20230276.  doi:10.7503/cjcu20230276
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n-Propylbenzene is a typical aromatic substitute component of Jet A, Jet A-1 and RP-3 aviation kerosene. In this work, the main oxidation reaction networks and the product distributions of n-propylbenzene at different temperatures, densities and equivalence ratios were investigated by ReaxFF based on reactive molecular dynamics simulation. The reaction kinetics theory was also employed to calculate the rate constants of n-propylbenzene oxidation. The results show that the consumption of n-propylbenzene mainly occurs in the alkyl side chain including six C—C and C—H bond fissions of unimolecular reactions and three H-abstraction reactions by O2 and other small radicals. Due to the lowest bond dissociation energy, the C—C bond fission adjacent to benzyl radical is the most important consumption channel but the contributions of all H-abstraction reactions are similar. The simulated temperature and density/pressure are positively correlated with the oxidation rate of n-propylbenzene, while the effect of equivalence ratio is heavily dependent on the system temperature. Additionally, the calculated apparent activation energies and pre-exponential factors are acceptable compared to the reported experimental results.

High-performance Cu-ZnO@SiO2 Nano-catalyst for CO2 Hydrogenation to Methanol
CHEN Hao, CHEN Gui, SONG Dandan, ZENG Yanhong, LIU Wenhu, ZHANG Ming
2023, 44(11):  20230268.  doi:10.7503/cjcu20230268
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Cu-based catalysts are widely employed for CO2 hydrogenation to methanol. However, their catalytic performance highly depends on supports. Herein, the nano-spherical SiO2 support was synthesized by the Stöber method and used as a component in Cu-ZnO@SiO2 catalyst. The catalyst was tested in hydrogenation of CO2 to methanol and compared with the Cu-ZnO catalyst(6.9% yield of methanol and 36.5% selectivity of methanol) prepared via conventional coprecipitation process. It was found that Cu-ZnO@SiO2 catalyst exhibits the best catalytic performance, the yield of methanol reached 11.1% with 88.2% selectivity of methanol at n(H2)/n(CO2)=3,230 ℃, 2.0 MPa and gaseous hourly space velocity(GHSV)=3600 mL·gcat-1·h-1. The catalysts were thoroughly characterized by X-ray diffraction(XRD), scanning electron microscope(SEM), X-ray photoelectron spectroscopy(XPS), tempera-ture-programmed reduction(H2-TPR) and CO2 temperature-programmed desorption(CO2-TPD). The results show that Cu-ZnO@SiO2 catalyst has higher Cu dispersion and CO2 adsorption capacity, and the addition of SiO2 increases the Cu+/Cu0 molar ratio on the catalyst surface, which affects the catalytic performance. The characterization analysis of Diffuse reflectance fourier transform infrared spectroscopy(DRIFT) showed that CO2 generated methanol on Cu-ZnO@SiO2 catalyst mainly through reverse water gas reaction(RWGS)+CO hydrogenation path.

Methane C—H Activation by Cyclo18 Carbon-based Single-atom Transition Metal(Os, Ir)
ZHANG Haiping, KONG Xue, XIA Wensheng, ZHANG Qinghong, WAN Huilin
2023, 44(11):  20230259.  doi:10.7503/cjcu20230259
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It is of great significance and challenge for the conversion and utilization of methane(the main component of natural gases) due to its high stability in chemistry. In order to breakthrough out it, the key is to develop the catalysts for methane C—H activation under mild conditions. Here, we investigated methane C—H activation over cyclo[18] carbon-based single-atom transition metal(TM=Os, Ir)(TMC18) by means of density functional theory(DFT). The results show that the activation barrier of methane C—H over TMC18 is significantly lower than TM itself, and the species CH3 resulted from methane C—H cleavage tends to bind more weakly with TMC18 than TM+ ions. The weakened interaction between CH3 and TMC18 favors to the CH3 desorption or further transformation into value-added chemicals. Thus, cyclo[18] carbon-based single-atom TM exhibits its promising ability to high-efficiently activate C—H of methane at mild conditions. The detailed analysis on the interaction of TM with cyclo[18] carbon indicate that cyclo[18] carbon is good in electron-storage/attraction by d-π conjugation of TM-cyclo[18] carbon, which leads to the decrease in barrier of methane C—H activation over cyclo[18] carbon-based TM.

Performance and Mechanism of Graphene-carbon Felt Composited Gas Diffusion Cathode for Hydrogen Peroxide Electrochemical Production
HU Hongsu, SHEN Chuanzhe, WANG Yuhang, WANG Qingqing, HE Shilong, LI Peng
2023, 44(11):  20230245.  doi:10.7503/cjcu20230245
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Graphene and Ketjen black composite carbon felt gas diffusion cathodes were prepared by impregnation-sintering by adjusting the amount of anhydrous ethanol, the mass ratio of graphene to polytetrafluoroethylene (PTFE), sintering temperature and other factors during method, and their microstructure and H2O2 electrochemical catalytic performance were compared. Due to the scaly microstructure and abundant oxygen-containing functional groups, graphene-carbon felt composite cathode has higher H2O2 yield than Ketjen black-carbon felt composite cathode. The H2O2 catalytic performance of graphene-carbon felt composite cathode was improved by regulating the preparation process, and the response mechanism of different manufacture parameters on the H2O2 catalytic performance of graphene-carbon felt composite cathode was studied by means of linear sweep voltammetry(LSV), electrochemical impedance spectroscopy(EIS), Fourier transform infrared spectroscopy(FTIR), X-ray photo- electron spectroscopy(XPS) and other testing methods. The research results show that when the addition amount of anhydrous ethanol is 60 mL, the mass ratio of graphene to PTFE is 3∶1, and the sintering temperature is 360 ℃, the prepared cathode has high conductivity and high surface C=O functional group content. After 90 min of electro-chemical reaction, the cumulative concentration of H2O2 can reach 427.63 mg/L. This cathode has strong cycling stability and high H2O2 generation efficiency, which has significant advantages over the widely used carbon black/ PTFE cathode. It is anticipated that this work could provide a theoretical basis and technical method reference for the efficient electrochemical production of H2O2 of gas diffusion cathodes based on graphene.

Effect of Mo2C/PE Separator on the Performance of Lithium Sulfur Batteries
WANG Qian, WEI Yi, JIA Hongsheng
2023, 44(11):  20230223.  doi:10.7503/cjcu20230223
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In order to enhance the protective effect of lithium metal negative electrodes and suppress the shuttle effect of polysulfides, the molybdenum based materials with low-cost and high Earth abundance were selected to synthesize molybdenum carbide(Mo2C) with spherical shell structure, and the molybdenum carbide modified polyethylene separators(Mo2C/PE) was prepared. The influence of Mo2C/PE separators on the performance of lithium sulfur batteries was analyzed. The results indicate that the good lithium affinity of Mo2C can induce uniform deposition of Li+ and inhibit the growth of lithium dendrites. The Mo2C/PE separator has a large specific surface area and porosity, which has a certain improvement effect on the volume changes caused by the charging and discharging process. Compared to the battery without PE separator, Li-Li symmetric battery using Mo2C/PE separator has smaller polarization voltage fluctuations and can stably cycle at higher current density. Lithium sulfur batteries equipped with Mo2C/PE separators have a specific discharge capacity of 1235.3 mA·h/g at a rate of 0.2C, and after 500 cycles, the discharge capacity can be maintained at 652.4 mA·h/g.

Glucose Production from Cellulose via Selective Hydrolysis in Molten Salt Hydrate
LIANG Haotong, LIN Jianying, YUAN Shaomin, MA Qiaozhi
2023, 44(11):  20230218.  doi:10.7503/cjcu20230218
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To address the challenges of the unclear mechanism of cellulose dissolution and hydrolysis in molten salt hydrate(MSH). This work systematically studied the hydrolysis of cellulose in molten salts hydrate consisting of different cations(e.g., Li+, Na+, K+, Zn2+ ), and anions(e.g., Cl, Br and I), and screened the best molten salt for cellulose hydrolysis, LiBr, and studied the effect of acidity on cellulose hydrolysis. The result indicated that the limited solubility of the cation Na+ and K+ resulted in the insufficient coordination between cations and oxygen atoms in the cellulose, which cannot provide sufficient Lewis acidity for glycosidic bonds cleavage. Additionally, the anion Cl in MSH has limited electronegativity, which cannot form massive hydrogen bonds with the hydroxyl groups in cellulose, resulting in a limited solubility and thereby caused negative effect on hydrolysis. Under the reaction conditions of 130 ℃ and 5 h in a non-acidified system, cellulose can be selectively hydrolyzed into water-soluble oligosaccharides and glucose with the yield of 57.2% and 29.0%, respectively. The results also show that the MSH can catalyze the cleavage of cellulose glycoside bonds and decrease the cellulose degree of polymerization(DP) in an 0.01%(HCl) dilute acidic MSH at 100 ℃ for 30 min ranging from 4 and 13. Improvement of acidity can enhance the cleavage efficiency of glycosidic bond cleavage. When the acidity increased to 0.1%(HCl), a high yield of glucose at 90.9% can be achieved at 100 ℃ for 30 min.

Morphology Controlled Synthesis of ZSM-22 Molecular Sieves and Their Catalytic Performance on Long-chain Bioalkane to Aviation Kerosene
ZHAO Chen, TAN Juan, HAN Jingjing, LIU Rui, FENG Chunshuo, LIU Jing
2023, 44(11):  20230208.  doi:10.7503/cjcu20230208
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In this paper, ZSM-22 zeolites with different crystal or aggregate morphologies, such as short rods, long needles, petals, thick rods, ellipsoids and coarse bundles, were synthesized through adding different additives, solvents or template agents. HZSM-22 catalysts with different morphologies were characterized by XRD, SEM, N2 physical adsorption, NH3-TPD and Py-IR techniques. The performance of HZSM-22 catalysts with different morphologies was evaluated on the hydrocracking and hydroisomerization of long-chain normal bio-paraffins obtained from the hydrodeoxygenated curcas oil to bio-jet fuel. The results showed that the catalyst C-4 with ellipsoid aggregate appearance was assembled by small crystals with a length of about 120 nm, which possesses a large surface area and plenty of B acid sites at the pore mouth of channel. On this basis, Pt/ZSM-22 catalysts were prepared by the equal volume impregnation method using HZSM-22 with different morphologies as support. The Pt/C-4 catalyst presented excellent hydrocracking and isomerization performance and stability. The conversion of long-chain normal bio-paraffins over Pt/C-4 reached 94.21%, and the yield of bio-jet fuel was as high as 47.87% with an iso/n-paraffin ratio of 6.0.

Polymer Chemistry
Self-assembly of PNDC-b-PTPE to Prepare Thin Films with Both Structure and Luminescent Color
DUAN Xiaoli, HAN Huimin, ZHAO Mingkun, REN Lixia
2023, 44(11):  20230291.  doi:10.7503/cjcu20230291
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Big steric monomer with aggregation induced emission tetraphenylethylene group, norbornenyl modified with tetraphenyl ethylene(NTPE), was designed and synthesized, dendronized block copolymer poly(decanephenyl terephthalate based norbornene)-block-poly(norbornenyl modified with tetraphenyl ethylene)(PNDC-b-PNTPE) was prepared by sequential ring-opening metathesis polymerization(ROMP) of NTPE and dendronized monomer with di-decanyl groups, decanephenyl terephthalate based norbornene(NDC). One-dimensional photonic crystal(1D PC) thin film with both structural color and luminescent emission was prepared by thin film self-assembly. The experimental results showed that the 1D PC thin film, which reflects blue color, was prepared by quick self-assembly of PNDC-b-PNTPE in tetrahydrofuran(THF), the maximum reflection wavelength(λmax) was 443 nm. Scanning electron microscopy image of the cross section of the 1D PC thin film showed that the PNDC-b-PNTPE self-assembled into lamellar structures with periodicity of 133 nm. Fluorescent emission spectrum showed that the luminescent emission of the self-assembled 1D PC thin film was 425 nm. The 1D PC thin film with both structural color and luminescent emission shows potential in display and anti-counterfeiting fields.

Protein Folding Assisted by Covalent Hydrogel Based on Amphiphilic Supramolecular
WANG Jiaxin, LIU Jia, QIN Jinmei, NYV Mondele Mbola, MENG Zihui, XUE Min
2023, 44(11):  20230250.  doi:10.7503/cjcu20230250
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A novel monomeric species, 2-{6-[3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido]hexylcarbamoyloxy} butyl acrylate(UPy-C6-HBA), was synthesized while 4-hydroxybutyl acrylate(HBA) was introduced to the intermediate compound 2-(6-isocyanatohexyl ureido)-6-methyl-4[1H] pyrimidinone(UPy-C6-NCO) which was obtained through the reaction of 2-aminomethyl-4-hydroxy-6-methylpyrimidine(MIS) with 1,6-hexane diisocyanate(HDI). UPy-C6-HBA together with acrylamide(AM) and NN'-methylenediacrylamide(Bis) was polymerized by UV-induced free radical polymerization method, yielding physically crosslinked hydrogels that possessed a homogenous porous architecture and pronounced swelling capacity. Lysozyme was incorporated within the hydrogel matrix containing UPy-C6-HBA monomer which in vitro refolding was facilitated via hydrophobic interactions. The effects of UPy-C6-HBA concentration, hydrogel dosage, lysozyme concentration and refolding temperature on the refolding rate of lysozyme were meticulously investigated. Remarkably, the supramolecular hydrogel comprising UPy-C6-HBA at a mass fraction of 15% exhibited a remarkable 41% enhancement in the refolding rate of lysozyme at 25 ℃ compared with the control. These findings unequivocally demonstrate the addition of UPy-C6-HBA monomer to the hydrogel matrix significantly improved the refolding rate of lysozyme, which is of great significance for the refolding of high concentration denatured lysozyme.

Fabrication and Performance of UV⁃curable Silicone Modified Polyurethane UV Curing Macroinitiators from Irgacure⁃2959
YUAN Hongping, ZHU Hongyu, SUN Nana, CHEN Jie, HUANG Chuanxia, LI Meijiang, LI Wenqing, LAI Guoqiao, YANG Xiongfa
2023, 44(11):  20230221.  doi:10.7503/cjcu20230221
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To overcome the disadvantages of small molecule ultraviolet(UV) initiators such as toxicity, having an unpleasant odor, easy to turn yellow and migrate from UV cured materials and to solve the oxygen resistance in UV curing industry, UVcurable silicone modified polyurethane UV curing macroinitiators were synthesized from 2hydroxy4'(2hydroxyethoxy)2methylacetone(Irgacure2959), castor oil, hydroxyhydrocarbon silicone oil, isophorone diisocyanate and hydroxypropyacrylate. Subsequently, it was adopted to prepare highly transparent UVcurable materials by UVcurable polyurethane acrylate prepolymers. The results showed that when the amount of UV initiator obtained was 3%(mass fraction) and the curing time was 70 s, the UVcurable materials prepared exhibited fairly good performance with pencil hardness of 2H—4H, transmittance above 80%, tensile strength about 26.4 MPa, elongation increased from 18% to 42%. The migration rate of Irgacure2959 was 7.2% and the UVcurable material prepared with it turned significantly yellow after UV aging for 4 min. By contrast, the migration rate of the UVcurable silicone modified polyurethane UV curing macroinitiators was as low as 2.1%, and the UVcurable material prepared with it turned slightly yellow even after UV aging for 14 min. It can be convinced that fabrication of UVcurable silicone modified UV curing macroinitiators is an effective strategy to reduce the migration rate of UV initiators and improve the UV resistance and flexibility of UVcurable materials.

Preparation, Properties and Shape Memory Mechanism of Polyacrylate-based Polymer Crosslinked by Self-assembled Core-shell Nano-microdomain
LI Mingfei, LYU Jianing, LI Xingjian, DING Xiaobin
2023, 44(11):  20230101.  doi:10.7503/cjcu20230101
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The polyacrylate-based shape memory polymer(SMP) with self-assembled core-shell nano-microdomains was prepared by UV-initiated free-radical polymerization of the active core-shell nanomicelles formed by self-assembly of active Pluronic F127 triblock copolymer end-capping acrylate groups as multifunctional nano-crosslinker and hydroxyethyl acrylate and acrylic acid as co-monomers. The thermal properties, dynamic thermo-mechanical properties and mechanical properties of the polyacrylate-based SMPs were characterized by differential scanning calorimeter, dynamic thermo-mechanical analyzer and universal tensile testing machine. The results showed that the glass transition temperature, room temperature modulus, modulus ratio of upper and lower glass transition, tensile strength and elongation at break of the SMPs decreased gradually with the decreasing concentration of acrylate monomer. The SMP system exhibited both high strength and high toughness. The shape fixity ratio(Rf), shape recovery ratio(Rr), and shape recovery rate(Vr) of the SMPs were quantitatively characterized. The results showed that when the monomer concentration exceeded 1.97 mol/L, the SMP exhibited excellent shape memory performance, with Rf of more than 97%, Rr of above 98% and Vr of over 8.8%/min. Finally, the shape memory mechanism of the SMP system was analyzed by stress relaxation.