Loading...

Table of Content

    10 August 2025, Volume 46 Issue 8
    Content
    Cover and Content of Chemical Journal of Chinese Universities Vol.46 No.8(2025)
    2025, 46(8):  1-6. 
    Asbtract ( )   PDF (20611KB) ( )  
    Related Articles | Metrics
    Articles: Inorganic Chemistry
    Aggregation Induced Emission Enhancement of Ligand-Engineered Au Nanoclusters
    YE Weiqing, LU Hui, CHEN Wanjing, LI Ningjing, ZHANG Yu, WANG Lihua, LI Jiang, ZHU Ying, LI Mingqiang, FAN Chunhai, JIA Sisi, CHEN Jing
    2025, 46(8):  20250100.  doi:10.7503/cjcu20250100
    Asbtract ( )   HTML ( )   PDF (5882KB) ( )  
    Figures and Tables | References | Supplementary Material | Related Articles | Metrics

    The aggregation-induced emission(AIE) properties of gold nanoclusters(Au NCs) exhibit significant potential for applications in bioimaging, chemical sensing, and optoelectronic devices. However, developing effective design strategies to achieve strong aggregation-induced emission enhancement(AIEE) in Au NCs remains a challenge. In this paper, we report a ligand engineering approach to achieve remarkable AIE enhancement in Au8 nanoclusters. The quantum yield of aggregated Au8 NCs showed a ca. 90-fold increase compared to their solution state, with corresponding emission intensity enhancement reaching ca. 560-fold. Through combined optical characterization and metastable component tracking in aggregated systems, we elucidate the underlying AIEE mechanism. Both AIEE and crystallization-induced emission enhancement(CIEE) were activated through ligand engineering, which facilitated (1) shortened inter-cluster distances(from 1.31 nm to 0.72 nm) and (2) effective suppression of intermolecular rotational/vibrational relaxation. This steric-hindrance-reduction strategy establishes a new paradigm for precise modulation of photoluminescence in gold nanoclusters across both aggregated and crystalline states.

    Analytical Chemistry
    Cataluminescent Sensing of 1,2-Epoxypropane Using Dy₂O₃/La₂O₃ Rare Earth Composite Oxides
    ZHANG Yuwei, DU Yihao, ZHANG Yantu, LI Yunyun
    2025, 46(8):  20250108.  doi:10.7503/cjcu20250108
    Asbtract ( )   HTML ( )   PDF (5445KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    In this study, we developed a high-performance cataluminescence(CTL) sensing platform based on Dy₂O₃/La₂O₃ rare-earth composite oxides for specific detection of 1,2-epoxypropane(PO). Through optimized composition regulation of the rare-earth oxides, the Dy₂O₃/La₂O₃ heterointerface demonstrated remarkable synergistic catalytic effects, achieving both high sensitivity(LOD=82.8 μmol/L) and exceptional selectivity(10-fold higher response to PO than interferents). Under optimal conditions(detection wavelength: 575 nm; temperature: 360 ℃; gas flow rate: 320 mL/min), the CTL intensity showed excellent linear correlation with PO concentration(y=701.25x+15085.19, R²=0.9969), with an ultralow detection limit(8.28×10⁻⁵ mol/L). The sensing system exhibited outstanding stability(RSD<3% over 11 cycles) and satisfactory recovery rates(96-108%). A "photoexcitation-oxygen activation-selective oxidation-characteristic luminescence" sensing mechanism was proposed. This work provides a novel strategy for developing rare-earth oxide-based sensing materials and offers an innovative solution for environmental VOC monitoring.

    Detection of Urea by Conductivity-regulated Bipolar Electrochemiluminescence
    YANG Bifang, GUO Xiaoge, DAI Xiaohui, YANG Weiqiang, NI Jiancong
    2025, 46(8):  20250101.  doi:10.7503/cjcu20250101
    Asbtract ( )   HTML ( )   PDF (2830KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    In this study, a bipolar electrochemiluminescence(BPE-ECL) sensing platform based on the regulation of conductivity was constructed for the detection of urea. An independent sensing cell and a reporting cell were built on the patterned BPE, and ruthenium bipyridine/tri-n-propylamine was used as the source of ECL. When urea at different concentrations is present in the sensing cell, urease specifically catalyzes the decomposition of urea, generating ions that promote an increase in the conductivity. Based on the charge balance of BPE, the ECL intensity from the reporting cell increases. Meanwhile, the ECL intensities increase following the enhancement of urea concentrations. Therefore, a BPE-ECL platform based on the regulation of conductivity was established for the detection of urea. Under optimal conditions, this sensing platform exhibits a good linear relationship for urea in the range of 10 nmol/L to 1 mmol/L, and the limit of detection is 0.19 nmol/L(S/N=3). The sensing platform was further applied to spiked recovery detection in human urine samples, showing good accuracy and anti-interference ability. This sensing strategy not only eliminates the need for exogenous electroactive indicators, but also effectively avoids the interference of complex biological samples with the signal reaction through the sensing-signal separation of BPE.

    Comprehensive Analysis of the Gene Expression Status in Wild and Drug-resistance Cell Lines of Colorectal Cancer
    YU Chengkun, ZHOU Haichao, ZHANG Congmin, REN Yan, LIU Siqi
    2025, 46(8):  20250049.  doi:10.7503/cjcu20250049
    Asbtract ( )   HTML ( )   PDF (3592KB) ( )  
    Figures and Tables | References | Supplementary Material | Related Articles | Metrics

    This study examined 3 colorectal cancer cell lines, HCT116, LoVo, and HT29, each of which contained both wild-type and Oxaliplatin/SN38-resistant strains. Transcriptomic and proteomic analyses were performed. By analyzing the differential gene expression between wild-type and resistant strains, it was found that the transcriptomic patterns of HCT116 and LoVo wild-type cell line appeared similar, whereas both were different from HT29. In view of different expression genes(DEGs) of the cell lines responding to oxaliplatin or SN38, the transcriptomes of wild cell lines were different from that obtained from the drug resistant cell lines. Moreover, among oxaliplatin resistant cell lines, the transcriptomic responses were consistent, but in SN38 resistant cell lines, the relevant changes were complicated, particularly in HT29 cells. Based on comparison of different expression proteins(DEPs) in these cells, DEPs were overlapped with DEGs somehow. In contrast to transcriptomes, the protein abundance in Lovo and HT29 was sensitively impacted by drugs, while the functional clustering derived from DEPs in LoVo and HCT116 was comparable. By analyzing the commonly regulated genes in both the transcriptome and proteome, we identified candidate drug resistance-related proteins. Specifically for drugs, the abundance responses of proteins in these cell lines initiated by oxaliplatin were significantly lower than these induced by SN38. Taking all analysis to gene expression status in wild and drug resistance cell lines together, this study indeed sets up a solid dataset to explore the molecular mechanism of drug resistance and provides an omic clue in colorectal cancer research.

    Organic Chemistry
    Catalyst-modulated Selective Hydrogen Transfer Reactions of Polyols with 2-Nitroaromatics
    ZHANG Yaoyao, LIU Shanshan
    2025, 46(8):  20250057.  doi:10.7503/cjcu20250057
    Asbtract ( )   HTML ( )   PDF (1404KB) ( )  
    Figures and Tables | References | Supplementary Material | Related Articles | Metrics

    The selective conversion of biomass-derived polyols into nitrogen-containing compounds remains a formidable challenge in sustainable chemistry. Although hydrogen borrowing strategies have emerged as environmentally benign alternatives to traditional reductive amination, precise control over selective C—C bond cleavage during polyol conversion persists as a significant difficulty. Herein, we report an approach utilizing distinct catalytic systems to regulate selective C—C bond cleavage of polyols, thereby generating diverse nitrogen-containing compounds. This system efficiently synthesizes quinoxaline and indole-type N-heterocyclic compounds under mild conditions without requiring external reducing agents. Substrate scope studies demonstrate that both electron-rich and electron-deficient aromatic amines and indole substrates afford the target products in moderate to excellent yields. This strategy overcomes the reliance of traditional reductive amination on harsh conditions and external reductants, thus providing a new, atom-economical, and environmentally benign pathway for biomass transformation.

    Synthesis of Aminoalkyl Naphthol Analogues and Their Anti-fungal and Nematicidal Activities
    ZHANG Qilin, SHI Yanchang, GAO Kun, WANG Linsong, SONG Yadong, WANG Yusen, LI Pengcheng, LIU Song, XING Ronge, SONG Lin, QIN Yukun
    2025, 46(8):  20250031.  doi:10.7503/cjcu20250031
    Asbtract ( )   HTML ( )   PDF (6686KB) ( )  
    Figures and Tables | References | Supplementary Material | Related Articles | Metrics

    A series of amino-alkyl naphthol compounds was synthesized through a one-pot threecomponent reaction, their antifungal activity against plant pathogenic fungi and nematicidal activity were evaluated. The results showed that compound 8 exhibited about 50% inhibitory activity against Alternaria alternate at concentrations ranging from 200 μg/mL to 25 μg/mL, and the inhibitory effect was not significantly correlated with concentration. In vivo antifungal experiments indicated that compound 8 at a concentration of 50 μg/mL had a therapeutic effect comparable to the positive control pyrimethanil. Additionally, in greenhouse test tube experiments, the synthesized compounds showed significant inhibitory activity against southern root-knot nematodes, with compound 10 significantly reducing the number of galls at a concentration of 10 μg/mL, achieving an inhibition rate of 90.91%, which is comparable to the positive control fluopyram. In summary, amino-alkyl naphthol compounds, as a new type of pesticide active substance, have potential dual effects of antibiosis and nematicide, and the aforementioned research provides new ideas for the development of environmentally friendly multi-target pesticides.

    Physical Chemistry
    Preparation of 2,5-Furandicarboxylic Acid by Electrocatalytic Oxidation of 5-Hydroxymethylfurfural with P-NiCoMo-LDH
    HUI Chenyang, XU Chenhui, YANG Yang, LIU Jialun, LI Yatai, GUO Zhenguo, YANG Zhenzhen, ZHANG Genlei
    2025, 46(8):  20250126.  doi:10.7503/cjcu20250126
    Asbtract ( )   HTML ( )   PDF (9710KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Recently years, research on the catalytic oxidation of 5-hydroxymethylfurfural(5-HMF) to synthesize 2,5-furandicarboxylic acid(FDCA) has garnered significant attention. Compared with conventional thermal catalytic methods, electrocatalytic oxidation of 5-HMF offers advantages such as mild reaction conditions and reduced environmental pollution, making it a promising green and sustainable alternative. A P-doped NiCoMo-layered double hydroxide(P-NiCoMo-LDH) material with a unique sea urchin-like morphology was synthesized via a two-step process involving solvothermal treatment followed by high-temperature calcination. Its catalytic performance in the electrocatalytic oxidation of 5-HMF to FDCA was systematically investigated. The composition, structure, and surface chemical properties of the material were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), and X-ray photoelectron spectroscopy(XPS). Additionally, its electrochemical performance was evaluated through linear sweep voltammetry(LSV) and electrochemical impedance spectroscopy(EIS). The results demonstrate that the catalyst exhibits outstanding electrochemical and catalytic performance. At an applied potential of 1.5 V(vs. RHE), the FDCA yield reaches 92.3%, with a Faradaic efficiency of 90.5%. Compared to undoped NiCoMo-LDH, these values represent increases of 44.3% and 40.5%, respectively. Furthermore, mechanistic studies and stability tests provide deeper insights into the catalytic mechanism of the P-NiCoMo-LDH material and its potential for FDCA synthesis.

    In⁃situ Construction of Co-MOFs/Carbon Fiber Composite Cathodes and their Efficient Degradation of Tetracycline in the Electro-Fenton System
    QIN Caiyi, LI Juan, LI Ying, ZHANG Jiuwen, LONG Hanyi, LI Xinyu, MI Nan, LIU Jinwei, LI Hua
    2025, 46(8):  20250118.  doi:10.7503/cjcu20250118
    Asbtract ( )   HTML ( )   PDF (5706KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    The traditional Fenton method catalyzes the H₂O₂ by Fe²⁺ to generate hydroxyl radicals (OH), which can efficiently degrade antibiotic organic pollutants in water. However, its wide application is limited by the large amount of iron sludge, the difficulty of Fe²⁺ regeneration and the problems of secondary pollution. The electro-Fenton technology combines electrochemistry and the Fenton oxidation process to significantly improve the efficiency of H₂O₂ activation. The use of cobalt-based metal organic frameworks(Co-MOFs) as electric Fenton catalysts has high catalytic activity and stability, which can avoid the generation of iron sludge and achieve the purpose of efficient degradation and removal of antibiotic organic pollutants in water. In this paper, Co-MOFs nanocrystalline materials were grown in situ on carbon fiber electrodes, and heterogeneous electric Fenton systems were constructed with the composite material as the cathode and platinum sheets as the anode. By adjusting the preparation method, the type of ligand, the ratio of ligand to metal, the calcination temperature, the system voltage, and the amount of H2O2 added, the optimal preparation conditions were explored: under the hydrothermal condition, Co-MOFs were synthesized by 1∶1 coordination of terephthalic acid and cobalt salt, which were grown in situ on a carbon fiber substrate, and calcined and activated under 100 ℃ in air. The optimal reaction conditions are: the voltage was -0.8 V and the H2O2 addition was 60 μL, and the degradation effect of tetracycline was 91% in 90 min.

    Synthesis of Nitrogen-doped Porous Molybdenum Carbide Nanorods and Their Electrocatalytic Hydrogen Evolution Performance in Acidic and Alkaline Media
    WANG Yitong, CAO Yuanyuan, ZHOU Lina, YE Rongrong, LI Di, LIU Xinxin, GUO Biao, ZHOU Lijing, ZHAO Zhen
    2025, 46(8):  20250095.  doi:10.7503/cjcu20250095
    Asbtract ( )   HTML ( )   PDF (8713KB) ( )  
    Figures and Tables | References | Supplementary Material | Related Articles | Metrics

    Water electrolysis for hydrogen production has been recognized as an ideal pathway toward scalable green hydrogen manufacturing, owing to its renewable feedstock utilization, zero carbon emission byproducts, and high-purity hydrogen output. As the pivotal half-reaction in water splitting, the hydrogen evolution reaction(HER) suffers from sluggish kinetics that fundamentally limits energy conversion efficiency. Consequently, developing HER electrocatalysts with combined high activity and operational stability remains a critical challenge for practical implementation. In this work, nitrogen-doped molybdenum carbide nanorods with hierarchical porous structures were synthesized by precisely regulating key synthesis parameters, including carbonization temperature and glucose content. Their phase composition, chemical state distribution, and morphological features were characterized via X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), nitrogen adsorption-desorption, Raman spectroscopy, scanning electron microscope(SEM), and transmission electron microscope(TEM). Electrochemical evaluations demonstrated that the optimized catalyst requires low overpotentials of merely 161 and 118 mV to achieve a current density of 10 mA/cm2 in 0.5 mol/L H2SO4 and 1 mol/L KOH, respectively. Remarkably, it exhibits exceptional operational stability, sustaining continuous HER operation for 200 h at 10 mA/cm2 in acidic media and 120 h under identical current density in alkaline condition.

    Electrochemical Removal of PFAS by Boron-doped Diamond Electrode
    ZHANG Senchong, LYU Jitao, WANG Sen, LYU Jilei, WANG Shaolong, WANG Yawei
    2025, 46(8):  20250096.  doi:10.7503/cjcu20250096
    Asbtract ( )   HTML ( )   PDF (5983KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    In this study, six boron-doped diamond(Nb/BDD) electrodes with different boron doping levels were prepared using niobium flakes as the substrate by microwave plasma chemical vapor deposition, and the effects of different boron doping levels on the electrochemical performance of Nb/BDD electrodes and their oxidation of perfluorooctanoic acid(PFOA) were investigated and applied to the electrochemical removal of different perfluorosulfonic acids(PFASs). The results showed that with the increase of boron doping level, the grain size of the Nb/BDD film gradually decreased and the electron transfer rate on the electrode surface gradually increased, but the decrease of film quality leads to the increase of its exfoliation rate. Na2SO4 was used as the electrolyte, and the Nb/BDD electrode as the anode was able to oxidize PFOA within 120 min at a current density of 30 mA/cm2. PFOA degradation rate to 78.3% and mineralization rate to 78.1% within 240 min. Among the six Nb/BDD electrodes prepared with different boron doping levels, the medium and low-doped Nb/BDD electrodes have higher degradation and mineralization ability for PFOA, indicating that the efficient electrochemical removal of PFAS can be achieved by regulating the boron doping level of BDD. The analysis of the degradation products indicated that the electrochemical degradation of PFOA follows the law of carbon chain step-by-step removal, in which the direct electron transfer between the anode and the pollutant is the key initiation step of degradation. The electrochemical degradation of PFSA and perfluorocarboxylic acid(PFCA) with different chain lengths reveals that the length of the carbon chain is positively proportional with the degradation rate and mineralization rate of PFAS, and thus the short-chain products generated by the degradation are the main reason for limiting the complete mineralization of PFAS. In the future, more attention needs to be paid to the efficient removal of short-chain and ultrashort-chain PFAS in order to meet the demand for the complete detoxification of PFAS through electrochemical technologies.

    Lithium/Sodium Atoms Adsorption and Migration on Silicene-Tin Disulfide Composite
    WEI Shiqian, LI Jiani, QIU Mei, LI Xian, CHEN Maoxia, FAN Qiang, TANG Fan, FAN Weifeng, HU Yu
    2025, 46(8):  20250054.  doi:10.7503/cjcu20250054
    Asbtract ( )   HTML ( )   PDF (7475KB) ( )  
    Figures and Tables | References | Supplementary Material | Related Articles | Metrics

    Silicene as a cathode material is promising for alkali metal atomic batteries. However, pure silicene could hardly meet the requirements of practical applications owing to the poor structure stability and conductivity which are related with the sp2-sp3 hybridization. It has been reported that the silicene and tin disulfide recombination and boron doping could solve above problems, but the effects of these two modification methods on other properties of silicene are still unclear, which is not conducive to effectively designing the atomic structure of the material. Considering the difficulty of alkali metal atom adsorption and migration is an important factor in evaluating the performance of negative electrode materials, the effects of the composites of silicene and tin disulfide and further introduction of boron on the adsorption and migration of lithium/sodium atoms were studied in this work based on the first principles. The calculated negative adsorption energies implied that lithium/sodium atoms can be stably adsorbed on the surfaces of different materials. It is attributed to the charge transfers between lithium/sodium atoms and substrates that promotes the formation of chemical bonds. However, these formed chemical bonds were different, which had an effect on the adsorption and migration of lithium/sodium atoms. For the surface of silicene, composite with tin disulfide can enhance the bonding between silicon and lithium/sodium, leading to a decrease in adsorption and migration energy barriers, which is beneficial for promoting the adsorption and migration of lithium/sodium atoms. The introduction of boron was able to further reduce adsorption energy through the formation of new bonds, while the migration energy barrier was undesirably increased. For the surface of tin disulfide, the composite of the two materials or the introduction of boron element had negligible effect on the bonding of lithium/sodium atoms, and there were no significant change in the migration energy barrier. Therefore, the composite material of silicene and tin disulfide was the best. The adsorption and migration of lithium/sodium atoms were easier on the silicene surface, and the tin disulfide surface enhanced the adsorption of lithium/sodium atoms and maintained their migration ability at the same time. It is expected that this work could gain an insight into the effect of different modification methods on the adsorption and migration behavior of alkali metal atoms and provide theoretical basis for designing effective electrode materials.

    Quaternary Ammonium Cation-assisted Synthesis of Sulfur Vacancy-rich MoS2 for Catalyzing Hydrogenation of Sulfur-containing Nitroarenes
    LING Zongpeng, CHEN Haitao, GAO Hongxia, DAI Huicong, ZHAO Zhenchao, YANG Qihua
    2025, 46(8):  20250048.  doi:10.7503/cjcu20250048
    Asbtract ( )   HTML ( )   PDF (7974KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    The catalytic hydrogenation of sulfur-containing nitroaromatic hydrocarbons to their corresponding amino compounds is a crucial reaction for achieving green transformation in pharmaceutical intermediates. However, the strong coordination of sulfur atoms poisons transition metal hydrogenation catalysts, suppressing their catalytic activity. Herein, we selected intrinsically sulfur-resistant MoS2 as the catalyst and modulated its sulfidation behavior by replacing ammonium ions in molybdate precursors with quaternary ammonium cations of varying organic chain lengths to synthesize corresponding MoS2 catalysts. Electron paramagnetic resonance(EPR) and O2 titration in situ infrared(IR) characterization reveal that edge sulfur vacancies in MoS2 increase with the elongation of quaternary ammonium salt carbon chains. In the hydrogenation of the model substrate 5-nitrobenzothiazole(NBZ), the catalyst’s activity is closely related to edge S vacancies. The optimized catalyst outperforms the currently reported Co-Mo-S catalysts. In a fixed-bed continuous flow reactor under 80 ℃, 0.3 MPa, the catalyst achieves a conversion efficiency of 49 mgNBZ·gcat‒1·h‒1, surpassing the performance of the supported noble metal catalyst Pt/TiO2 under identical conditions. This study demonstrates that long-chain organic quaternary ammonium cations significantly enhance edge S vacancies in MoS2, highlighting their potential application value in hydrogenating sulfur-containing nitroaromatic compounds.

    Preparation and Anti-pollution Properties of Carbonized Rice Husk/Polypyrrole Janus Solar Evaporator
    WANG Zhenyu, FANG Wei, ZHAO Lei, CHEN Hui, WANG Daheng, HE Xuan, DU Xing, LI Weixin
    2025, 46(8):  20250019.  doi:10.7503/cjcu20250019
    Asbtract ( )   HTML ( )   PDF (14388KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Harvesting clean water from seawater and wastewater based on solar-driven evaporators is emerging as one of the most promising ways to alleviate the shortage of water resources today. However, it also faces a typical defect of massive deposition of salts and pollutants in the functional evaporator, which generally influences the cyclic evaporation performance of the device. To address this problem, in this work a featured foam with a 3D porous structure was first prepared by combining polyurethane foam and carbonized rice husk powders. Then, the hydrophobic polypyrrole was introduced in the upper layer of this foam matrix to construct a Janus solar evaporator with asymmetric wettability while the upper layer shows hydrophobicity and the lower layer allows hydrophilicity. The results indicated the Janus solar evapovator demonstrates a maximum brine evaporation rate of 1.33 kg·m‒2·h‒1 and wastewater evaporation rate of 1.29 kg·m‒2·h‒1 under solar irradiation of 1 kW/m2, combining with good cycle stability. In addition, the introduction of organic polyurethane networks also endows the Janus evaporator with excellent structural stability, which can be fabricated and tailored to various sizes and shapes for large-scale application.

    Performance of CsPbI3 Perovskite Solar Cell Improved by Small Molecules of Triphenylamine Containing Pyridine Groups
    LYU Haijun, WANG Shenggang, MA Jiazhuo, HAO Yanzhong
    2025, 46(8):  20250018.  doi:10.7503/cjcu20250018
    Asbtract ( )   HTML ( )   PDF (5425KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    In this paper, two novel small-molecule triphenylamine derivatives NN-bis(4-methoxyphenyl)-4-(4- pyridyl) aniline(H432) and NN-bis(4-methoxyphenyl)-4-[4-(cyano)-3-pyridyl] aniline(H462), were synthesized by classic Suzuki-Miyaura and Ullmann coupling reactions. The small-molecule derivatives were deposited onto FTO/c-TiO2/m-TiO2/CsPbI3 composite films with crystal modification and surface post-treatment modification to fabricate CsPbI3 perovskite solar cells. The resulting devices were characterized and tested by SEM, J-V curves, and electrochemical impedance spectroscopy. The results show that the CsPbI3 perovskite solar cells prepared by surface post-treatment modification exhibits a significant increase in power conversion efficiency(PCE). Specifically, the PCE of CsPbI3 perovskite solar cells modified with 0.05 mol/L H432 increases from 12.44%(control device) to 15.54%, while the PCE of those modified with 0.05 mol/L H462 improves from 12.44% to 15.66%.

    Polymer Chemistry
    Preparation of Amine-capped Functionalized Trans-1,4-poly(butadiene-co-isoprene) Rubber and Coordination Chain Transfer Mechanism
    LUO Shufang, ZHAO Yuanjin, WANG Shuo, ZHOU Runchaun, YANG Xia, HE Aihua
    2025, 46(8):  20250067.  doi:10.7503/cjcu20250067
    Asbtract ( )   HTML ( )   PDF (2672KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    The chain-end functionalized rubbers play important roles in improving the filler dispersion and increasing the interaction force between rubbers and filler particles, both of which affect the properties of the final products. In this paper, amine-capped trans-1,4-poly(butadiene-co-isoprene) copolymers(F-TBIR) with controllable composition and micro-structure were synthesized through one-step coordination chain transfer polymerization by using heterogeneous TiCl4/MgCl2 type Ziegler-Natta catalyst with dicyclohexylamine(DCHA) as chain transfer agent. The effects of the amount of DCHA and co-catalyst triethylaluminum(AlEt3) on the the catalytic efficiency, amine-capped efficiency(CE, %) and chain micro-structure of the F-TBIR were investigated. The results indicated that DCHA did not change the stereo-regularity of the catalytic species. With the increase in DCHA dosage, the catalytic efficiency and molecular weight of the copolymers decreased, while CE increased significantly. With the increase in the amount of AlEt3, the catalytic efficiency initially increased then subsequently decreased, and the molecular weight of polymer and CE gradually decreased. Under the specified experimental conditions, the chain transfer constants of DCHA and AlEt3 were 0.0537 and 0.016, respectively. Combined with density functional theory(DFT) simulation, the chain transfer mechanism of DCHA and AlEt3 in the diene coordination polymerization catalyzed by heterogeneous Ziegler-Natta catalyst was discussed. This work provides a straightforward and feasible strategy for developing chain-end functionalized synthetic rubber.

    Structure and Properties of Polyester Hybrid Materials Directly Synthesized from Monomers
    LI Yantong, LIANG Qianqian, HE Li, LONG Xinyi, ZHANG Jiayu, LI Jiale, SUN Nan, ZHANG Quanping
    2025, 46(8):  20250060.  doi:10.7503/cjcu20250060
    Asbtract ( )   HTML ( )   PDF (3832KB) ( )  
    Figures and Tables | References | Supplementary Material | Related Articles | Metrics

    In polymer hybrid materials, a small quantity of inorganic components can significantly enhance physical properties such as mechanical and dielectric energy storage. However, traditional processing strategies like solution blending present complex procedures, high carbon emissions, and scalability challenges. This study employs a dual in situ strategy to directly synthesize polyester hybrid materials from organic-inorganic monomers, meanwhile spectroscopic analysis is utilized to investigate molecular structural evolution from monomers to the hybrid materials. The results demonstrate polyester in situ polymerization synchronizes with in situ growth of inorganic components during synthesis. More importantly, molecular-scale interdiffusion between polymer chains and inorganic components establishes a characteristic organic-inorganic hybrid structure. Tensile strength and elongation at break increase from 58.23 MPa and 17.14% for pure polyester to 68.98 MPa and 33.69%, respectively. The dielectric constant reaches approximately 2.1 times to that of pure polyester, while breakdown strength improves from 235.03 MV/m to 418.38 MV/m at 100 ℃. Consequently, the energy storage density surges from 5.38 J/cm³ to 10.64 J/cm³, representing a 97.77% enhancement. This work provides a low-carbon fabrication strategy for high-performance polyester hybrid materials, which expands functional development avenues and application potential for polyester-based materials.