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    10 April 2024, Volume 45 Issue 4
    Content
    Cover and Content of Chemical Journal of Chinese Universities Vol.45 No.4(2024)
    2024, 45(4):  1-6. 
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    Article: Inorganic Chemistry
    Lanthanum-supported Porous Carbon Composite Electrode Material Prepared by Rice Husk Char
    SUI Guanghui, CHENG Yanyan
    2024, 45(4):  20240012.  doi:10.7503/cjcu20240012
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    In this paper, a high value-added utilization method of rice husk char was proposed to prepare lanthanum-supported porous carbon composite electrode materials(La/PCs). A series of La/PCs were prepared via in situ activation/loading method. The effects of calcination temperature and impregnation ratio on the adsorption and electrochemical properties of La/PCs were investigated. X-Ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), scanning electron microscope-energy dispersive spectrometer(SEM-EDS) and Brunauer-Emmett-Teller surface area(BET) were used to study the metal structure, valence state, element compositions and surface morphology of those La/PCs. It was analyzed that the possible relationship between pore structure and capacitance value. As a result, the La/PC_900/10 exhibited high gravimetric capacitance of 269.45 F/g in 6 mol/L KOH electrolyte. At 0.5 A/g, the assembled symmetric supercapacitor presented a superior gravimetric energy density of 23.45 W·h/kg at 0.70 kW/kg and the capacitance retention rate was 86.41% after 5000 cycles. The favorable capacitive behavior of La/PC_900/10 demonstrated its potential as carbon-based electrode applied in high performance supercapacitors. This paper provides a feasible path for the utilization of rice husk char and the application of lanthanum in the field of new energy materials.

    Analytical Chemistry
    Graphene⁃gold Nanomaterial Modified Electrode for the Detection of L-Tyrosine
    MA Qinzheng, WANG Wei, LIANG Xuting
    2024, 45(4):  20230521.  doi:10.7503/cjcu20230521
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    Using a green and simple electrochemical method, a reduced graphene oxide-gold nanocomposite thin film was prepared for the detection of L-tyrosine(L-Tyr). The modified electrode was characterized via scanning electron microscopy(SEM), cyclic voltammetry(CV), and electrochemical impedance spectroscopy(EIS). The electrochemical behavior of L-Tyr on the modified electrode in 0.1 mol/L phosphate buffer solution was investigated using differential pulse voltammetry(DPV). The results demonstrated a significantly enhanced voltammetric response of L-Tyr on the modified electrode compared to a bare glassy carbon electrode(GCE). Optimization of the composite film’s thickness, pH of the supporting electrolyte, deposition potential, and accumulation time were carried out. Under the optimal experimental conditions, the oxidation peak current of L-Tyr exhibited a good linear relationship within the concentration ranges of 0.1—50 μmol/L and 50—1000 μmol/L using DPV. Moreover, the sensor demonstrated a detection limit of 50 nmol/L, a sensitivity of 0.553 μA·μmol·L‒1, and displayed excellent repeatability, stability, and anti-interference properties.

    Preparation and Application of Imidazole-based Ionic Liquid and Amide Bipolar Groups Co-embedded Hydrophilic C18 Silica Gel Stationary Phase
    CHEN Beiyi, GUAN Wenna, JIN Zhao, LIU Tingting, ZHOU Rui
    2024, 45(4):  20230503.  doi:10.7503/cjcu20230503
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    In this work, octadecyl-modified silica chromatographic stationary phases with amide and imidazole-based ionic liquid bipolar groups co-embedded were prepared by stepwise bonding and two stationary phases with different anionic coordinations(Sil-IL-AMC18-Cl and Sil-IL-AMC18-Tf2N) were prepared by ion-exchange, which were characterized by means of infrared spectroscopy and elemental analysis. Both stationary phases showed C=C stretching vibration peaks and C=N bending vibration peaks on the imidazole ring at 1460 and 661 cm‒1, and asymmetric and symmetric stretching vibration peaks of ─CH at 2927 and 2856 cm‒1, which proved the bonding of amino-imidazole ionic liquid. And the original 919 cm‒1 of primary amine N─H out-of-plane deformation vibration peak disappeared, indicating that octadecanoyl chloride is bonded with amino. The results of elemental analysis showed that Sil-IL-AMC18-Cl contained 3.07% of nitrogen, 16.73% of carbon and 3.07% of hydrogen, and Sil-IL-AMC18-Tf2N contained 2.88% of nitrogen, 15.98% of carbon and 2.95% of hydrogen, which indicated that Sil-IL-AMC18-Cl and Sil-IL-AMC18-Tf2N chromatographic stationary phases were prepared. The chromatographic separation modes and performance of Sil-IL-AMC18-Cl and Sil-IL-AMC18-Tf2N stationary phases were investigated, and the results showed that: (1) the two stationary phases had higher column efficiency than commercial C18 columns in the reversed-phase chromatographic mode(RPLC); (2) since the stationary phase has a bipolar group, it has a stronger hydrophilic ability compared to the traditional hydrophilic modified C18 silica stationary phase, and thus hydrophilic chromatographic mode(HILIC) can be realized; (3) simultaneous separation of hydrophilic and hydrophobic substances in mixed reversed-phase/hydrophilic(RPLC/HILIC) chromatographic mode. It was found that Sil-IL-AMC18-Cl stationary phase had stronger hydrophilic properties compared to Sil-IL-AMC18-Tf2N stationary phase, so in the HILIC chromatographic mode Sil-IL-AMC18-Cl stationary phase was used for the separation of 8 base nucleosides, which could realize the baseline separation of this kind of strong hydrophilic substances, and the RSD of the injection repeatability was 0.03%—0.25%(n=9); in the RPLC chromatographic mode, Sil-IL-AMC18-Tf2N stationary phase was used for the separation of 6 anilines, which not only could realize the baseline separation, but also improved the peak trailing problem of anilines, and the RSD of the injection repeatability was 0.05%—0.10%(n=9).

    Organic Chemistry
    Green Synthesis of Alkyl Thioesters in Water
    YAN Xiaoyu, CHEN Yuying, ZHAO Mei, YUAN Yiyun, BIAN Jiakun, MA Xiantao
    2024, 45(4):  20240006.  doi:10.7503/cjcu20240006
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    A new, green and extra additive-free synthesis method of alkyl thioesters in water media was developed in this paper. By using alkyl halides and thioamide as the raw materials, the reaction can proceed smoothly in aqueous phase for 4 h, to afford the target thioester products with high yields, and the method can be compatible with various functional groups. Compared with the available methods, this method has the advantages of simple experimental operation, green and high efficiency, good atomic economy, and can easily be scaled up in gram scale, and has high practical application value.

    Effect of Metal Ions on the Catalytical Activity of a DMSO-dependent RNA-cleaving DNAzyme
    CUI Li, LI Suhui, ZHENG Xing, CHANG Tianjun, BING Tao
    2024, 45(4):  20240004.  doi:10.7503/cjcu20240004
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    Engineering RNA-cleaving DNAzymes(RCDs) and RCD-based molecular devices that are highly functional in high content of organic co-solvents may not only expand the ability of DNAs as enzymes, but also promote functional nucleic acids for novel applications. In this work, we have investigated the requirement of divalent metal ions for a dimethyl sulfoxide(DMSO)-dependent RCD(named E3) that we previously reported. The divalent metal ions were proved to be crucial for E3 to function in 35%(volume fraction) DMSO, and the metal ions with the ability to activate E3 followed the order: Zn2+, Mg2+>Fe2+>Pb2+>Mn2+>Co2+. The rate-pH profile of E3 in Mg2+ showed a “bell” shaped curve with a plateau at the pH range from 7.0 to 9.0, yet a sharp peak at pH value of 7.0 in Zn2+. Moreover, both Zn2+ and Mg2+ bound to E3 at a number ratio of 1∶1. We also observed that E3 could be activated by Fe2+ in 35% DMSO, but quickly inactive by the rapid oxidation of Fe2+ to Fe3+. This inactivation of E3could be further rescued by the addition of ascorbic acid. In addition, the catalytic activity of E3 in the presence of Zn2+ or Mg2+ was sharply inhibited with the competition of Cu2+, Ni2+, and Fe3+. These results are helpful for understanding the characterization and catalytical mechanism of the DMSO-dependent RCD.

    Design, Synthesis and Anti-cervical Cancer Activity of Piperine-bicycloamide Derivatives
    WANG Xiujun, JIANG Wentao, HE Jingliang, CHEN Huijie, QIAO Yue, WANG Dewei, WANG Bingyan, HOU Xiao, LIU Wei, GENG Ting, ZHANG Siyi, LIU Xing, MA Shaojie, LIU Bin, YANG Mingli, JI Jing
    2024, 45(4):  20230520.  doi:10.7503/cjcu20230520
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    In this paper, a series of piperine-dicycloamide derivatives was synthesized using piperine as parent nucleus, and their structures were confirmed by means of nuclear magnetic resonance hydrogen spectroscopy (1H NMR), nuclear magnetic resonance carbon spectroscopy(13C NMR) and high-resolution mass spectrometry(HRMS). Methyl thiazolyl tetrazolium(MTT) assay showed that these compounds had good inhibitory effects on kidney cells(293T), cervical cancer(HeLa) and breast cancer(MD-MB-321). Most derivatives had better inhibitory activity on HeLa cells than positive controls fluorouracil(5-FU)and piperine, and compound 6b had the highest anti-proliferative activity on HeLa cells. The half maximal inhibitory concentration(IC50) of MDA-MB-321 cells was 3.49 μmol/L, and the IC50 of MDA-MB-321 cells was 20.89 μmol/L. The mechanism study showed that compound 6b not only effectively inhibited the migration, invasion, adhesion and cloning ability of HeLa cells, but also showed a strong inhibitory effect on the growth of xenografts of HeLa cells. Therefore, compound 6b has the potential to be a lead compound in tumor therapy.

    Catalytic Synthesis of N-methylindopregnenolone Compounds Based on Diosgenin and Their Anti-tumor Activity
    DONG Yuan, MA Yangmin, MA Siyue, SUN Renwei
    2024, 45(4):  20230449.  doi:10.7503/cjcu20230449
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    The D-ring C16 position of 16-dehydropregnenolone acetate(16-DPA), a precursor of steroidal drugs, was modified using N-methylindole, and the inexpensive catalytic system of ZrCl4-ethyl acetate was employed to synthesize sixteen (3β-acetyloxy-16α-3'-indolopregnenolone compounds) as well as to synthesize six 3β-hydroxy- 16α-3'-indolone pregnenolone derivatives. The method has the advantages of high yield, good stereoselectivity and substrate adaptability. Twenty-two compounds were tested for antitumor activity in triple-negative breast cancer cells (MDA-MB-231) by thiazolyl blue(MTT) assay. The preliminary test results showed that among the 3β-acetoxy- 16α-3'-indolopregnenolone compounds, compounds 6h and 6i had better cancer inhibitory activities against MDA-MB-231 cancer cells with median inhibition concentration (IC50) of 18.07 and 23.22 μmol/L, respectively, whereas all of compounds 7a—7f had better cancer inhibitory activities against MDA-MB-231 cancer cells, among which compound 7e showed the best antitumor activity with an IC50 of 12.50 μmol/L. These compounds provide some references for drug screening.

    Physical Chemistry
    Fe-promoted Pt@CeO2 Catalysts for CO2 Hydrogenation to C1 Products
    WANG Zijian, LI Yuou, ZHANG Lingling, WANG Xiao, SONG Shuyan, ZHANG Hongjie
    2024, 45(4):  20230480.  doi:10.7503/cjcu20230480
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    Transition metal promoters were introduced on the surface of the Pt@CeO2 core@shell nanospheres, and the effects of different transition metals on the CO2 hydrogenation performance were investigated. The results show that the introduction of Fe species has the best effect on the enhancement of the hydrogenation performance, with a liquid C1 yield of 6.34×10-2 mmol·gcat.-1·h-1. Transmission electron microscopy(TEM), X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), N2 adsorption-desorption experiments, CO2 temperature-programmed desorption(CO2-TPD), and H2 temperature-programmed reduction(H2-TPR) experiments reveal that Fe promoter was dispersed on the surface of Pt@CeO2, and Fe promoter decreases the charge density of Pt, generating more Pt2+ species and improving the selectivity of methanol. In addition, it also facilitates the formation of more oxygen vacancies(Ov), which in turn facilitate the adsorption of CO2 as well as the subsequent hydrogenation reaction, and improve the catalytic activity.

    Highly Selective Hydrogenation of Adiponitrile to Hexamethyleneimine Catalyzed by Carbon Nitrogen Composited Nickel Catalysts
    ZHANG Chenyang, JIA Chenxu, HUANG Jun
    2024, 45(4):  20240003.  doi:10.7503/cjcu20240003
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    Hexamethyleneimine(HMI) is a crucial intermediate in the production of pharmaceuticals and agrochemicals, including penicillin, herbicides, and fungicides. In this study, supported Ni-based catalysts were prepared using solvent-assisted mechanochemical ball milling and pyrolysis, and the catalytic performance for the hydrogenation of 1,6-adiponitrile(ADN) to HMI was evaluate. The results demonstrated that the supported Ni-based catalyst Ni/IM-C(R) exhibited high activity for the hydrogenation of ADN to HMI in 98% yield. The catalyst Ni/IM-C(R) was prepared by co-ball milling nickel acetate, 2-methylimidazole and activated carbon, followed by calcination in N2 and then reduced by H2. The surface structures and the chemical properties of the Ni/IM-C(R) catalyst were characterized via various techniques, including X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, transmission electron microscope, and N2 adsorption-desorption measurements. The characterization results indicated that nitrogen-doped carbon improved the dispersion of Ni nanoparticles in the Ni/IM-C(R) catalyst. The catalyst Ni/IM-C(R) displayed small Ni nanoparticles with high surface, which directed the high activity for the hydrogenation of ADN to HMI. Without additives, the Ni/IM-C(R) catalyzed hydrogenation of ADN exhibited excellent activity and high selectivity towards HMI. The Ni/IM-C(R) catalyst is stable and recyclable for several times without deactivation. The Ni/IM-C(R) catalyst is simple to be prepared and the Ni/IM-C(R) catalyzed hydrogenation of ADN is promising for industrial applications.

    Theoretical Study of Structure, Spectra and Quantum Efficiency for a Series of Iridium(III) Complexes with the Cyclometalating Ligand
    NIE Jianhang, WANG Tianqi, JIN Li, ZHANG Jianpo, ZHANG Hongxing, BAI Fuquan
    2024, 45(4):  20240036.  doi:10.7503/cjcu20240036
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    A series of cyclometalated iridium(III) complexes [(C^N)2Ir(A^A)] [C^N=ptaz(1, 2, 4), mhtz(3), ptaz=3,4,5-triphenyl-4H-1,2,4-triazole, mhtz=1,3-dimethyl-5-phenyl-1H-1,2,4-triazole; A^A=pzpy(1), npzpy(2, 3), bicb(4), pzpy=2-(1H-pyrazol-1-yl)pyridine, npzpy=4-dimethylamino-2-(1H-pyrazol-1-yl)pyridine, bicb=3,3′-methylenebis(1-methyl-1H-imidazole- 3-ium2-ide)] was investigated theoretically to explore their structures, spectroscopic properties and quantum efficiencies. The exploration of calculation methods shows that, the ground state structure optimized based on B3LYP functional and the excited state structure obtained by configuration interaction singles(CIS) method yield more accurate absorption and emission spectra. The lowest energy absorption and emission of complexes 1—4 at 408, 376, 382, 365 nm and 503, 506, 468, 511 nm, respectively. The HOMOs of complexes 1—4 are dominantly localized on the d(Ir) and π(C^N) ligand, while the LUMOs of complexes 1—3 are composed of π*(A^A) ligands, however, the LUMO of complex 4 resides on the π*(C^N) ligand. Therefore, the lowest energy absorption and emission of complex 4 exhibit mixed transition properties from metal to ligand and intra-ligand(MLCT/ILCT) that differ from complexes 1—3, the introduction of non-conjugated N^N ligands significantly weakens their contribution in the transition process. The quantum efficiency of complexes 1—4 depends on the magnitude of the non-radiative rate constant knr, this is consistent with their contribution to reorganization energy of 4569 cm‒1(3)>2583 cm‒1(1)>1232 cm‒1(2)>975 cm‒1(4), this indicates that the size of the main-ligand and the conjugation ability of the auxiliary ligand can both affect the phosphorescence quantum efficiency of these complexes.

    Electrodeposited NiCu Alloy Anchored Co2P Nanowires Enhancing Hydrogen Evolution Reaction by Modulating Electronic Structure
    LIU Wenhuan, WANG Kangkang, DOU Jiayang, ZHANG Tongchen, DONG Sheying
    2024, 45(4):  20240005.  doi:10.7503/cjcu20240005
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    The development of efficient and stable hydrogen evolution reaction(HER) is the key to realize the widespread industrial application of electrolytic water technology. In this paper, HER catalysts CuAl@Co2P/NF with three-dimensional highly dispersed non-homogeneous phase were synthesized by hydrothermal-pyrolysis-electrodeposition using nickel foam(NF) as substrate. The formation of heterojunction between crystalline and amorphous surfaces increases the active sites of the catalyst itself, and the synergistic effect between the elements makes the Co atoms in the system rearrange their electrons outside the nucleus, reducing the adsorption capacity for the adsorbed H*, and accelerating the reaction kinetics in the process of hydrogen precipitation reaction. The catalyst exhibited favorable HER activity and stability in both alkaline and acidic environments, and the overpotential required to drive a current of 10 mA/cm2 was measured at 83 and 27 mV, respectively, while the potential remained essentially unchanged after continuous operation for 72 h in an alkaline environment. This work is informative for the construction of HER catalysts with highly dispersed non-homogeneous phase pairs.

    Preparation and Properties of n-C20@TiO2-x Phase Change Microcapsules and Thermoregulated Down Feather
    YAN Fangfang, XU Yimei, LI Lingang, YU Xueyong, CAI Yibing
    2024, 45(4):  20230501.  doi:10.7503/cjcu20230501
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    The phase change microcapsule of n-C20@TiO2 with titanium dioxide(TiO2) as shell and n-eicosane (n-C20) as core was prepared through sol-gel method. The microcapsule of n-C20@TiO2-x was obtained by reduction reaction on TiO2 shell with hydrazine hydrate(N2H4·H2O) solution. Then, down feather(DF) with thermal storage and temperature regulation(n-C20@TiO2-x /DF) was fabricated by combining with n-C20@TiO2-x using waterborne polyurethane(WPU) as medium. The structural morphology and thermal properties of microencapsulated phase change materials(MEPCMs) and n-C20@TiO2-x /DF were characterized by Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy(FESEM), X-ray diffractometer(XRD), X-ray photoelectron spectroscopy(XPS) and differential scanning calorimetry(DSC), etc.. The results showed that the particle size of n-C20@TiO2-x was about 309 nm, and heat enthalpy was increased from 80.2 J/g(n-C20@TiO2) before modification to 106.1 J/g, which exhibited good thermal stability. The heat enthalpy of obtained thermoregulated DF with 30% n-C20@TiO2-x was ca. 18.7 J/g, and could still reach 10.6 J/g after 5 times of washing. It provided a strategy for the investigation of microcapsule modification and functional down feather materials, which was conducive to broaden the application of phase change materials in the traditional textile field.

    Density Functional Theory Analysis of Coadsorption Behavior of Cl2 and O2 on TiC(100) Surface
    CHEN Rong, WEN Liangying, YUE Dong, YANG Zhongqing
    2024, 45(4):  20230497.  doi:10.7503/cjcu20230497
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    Based on the first-principles ab initio calculation method of density functional theory(DFT), the coadsorption model of Cl2 and O2 molecules on the TiC(100) intact surface was established. The reaction mechanism of Cl2 and O2 molecules on the TiC(100) intact surface was studied by analyzing adsorption energy, charge density, partial density of states(PDOS) and other parameters. And it was found that the dissociated Cl and O atoms bond with the TiC(100) surface atoms, thus breaking the Ti—C bond. The Cl2 molecule acts as an electron acceptor during the adsorption process, obtaining electrons contributed by the Ti atom that bonds with it, and the O2 molecule also acts as an electron acceptor during the adsorption process, obtaining electrons contributed by the C atom. On the surface of TiC(100), the number of electrons occupied in the bonding orbitals of Ti—C decreases, and the number of electrons occupied in the antibonding orbitals increases, which indicates the bonding between Ti and C atoms is weakened. At the same time, Ti3d has orbital overlapping hybridization with Cl3s and Cl3p, and there are strong formant peaks in O2p and C2p orbits, and Cl and O atoms interact strongly with TiC surfaces.

    Preparation of P-doped Coal Pitch-based Porous Carbon and Its Adsorption Performance for Broad-spectrum Antibiotics in Wastewater
    YU Moxin, SHI Wenxu, SUN Yuhang, ZHANG Chen, WANG Xiaoting
    2024, 45(4):  20230481.  doi:10.7503/cjcu20230481
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    P-doped porous carbon(CPC x ) was prepared by one-step method with coal tar pitch as carbon, sodium hypophosphite monohydrate as phosphorus sources and MgO as template coupled with KOH activation. CPC x were characterized by SEM, BET, FTIR, XPS, and the adsorption properties of porous carbon for oxytetracycline and chloramphenicol were investigated. When the mass ratio of coal tar pitch to phosphorus source is 2∶1, the BET results show that the total specific surface area and the microporous specific surface area of as-made CPC2.0 are 2739 and 2353 m2/g, respectively, and the average pore size is 3.78 nm. The results of FTIR indicate that the phenyl absorption peak for CPC x is deepened compared to the original carbon, as well as a new stretching vibration peak of P—O is displayed. The XPS results demonstrate that the P content and the most stable C3—P=O functional group content of phosphorus configuration on the surface of carbon materials are 0.45% and 37.7%(molar fraction). The adsorption process of antibiotics by CPC2.0 can be better described by Langmuir model and pseudo second-order kinetic model, and the maximum adsorption capacities of CPC2.0 for oxytetracycline and chloramphenicol are 1780 and 1122 mg/g, respectively, showing better adsorption performance.

    Polymer Chemistry
    Properties of Bionic Rubber Reinforced by Silica/carbon Black
    WANG Ke, WANG Yuge, HE Tiancheng, FENG Xueyang, PAN Lijia, CHEN Siyuan, YIN Yuan, SUN Hongguo, ZHENG Yafang, WEI Lai, SUN Zhaoyan
    2024, 45(4):  20230512.  doi:10.7503/cjcu20230512
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    Silica/carbon black(CB) mixed filler is one of the fastest-developing novel reinforcement agents for rubber materials in recent years, primarily employed to enhance the dynamic performance of rubber materials. In order to explore the influence of hybrid filler ratios and mixing processes on the dynamic and static mechanical properties of bionic rubber, two sets of experiments were designed: (1) with a fixed mixing time of 6 min, the bionic rubber was filled with silica/CB fillers at different mixing ratios, and a systematic study of properties, such as dispersion, tensile strength, fatigue and rolling resistance of the bionic rubber was conducted. The results show that when the mass fraction of silica in the fillers is less than approximately 50%, the tensile strength decreases with increasing the silica content, attributed to the decrease in the maximum cross-linking degree of molecular chains. However, with a further increase in silica content, the dispersion grade of vulcanizate increases from about 1 to about 9, leading to a reduction in filler agglomerate size and a significant increase in elongation at break and stretching fatigue life. (2) Under fixed mixing ratio conditions(mass fraction of silica in the fillers is 75%), the influence of mixing time on its dynamic and static mechanical properties was studied. The results show that within the studied mixing time range of 2—10 min, 4 min mixing significantly increases tensile strength, 300% modulus, and elongation at break, while reducing rolling resistance. This is mainly attributed to the larger maximum cross-linking degree of molecular chains and higher dispersion level and dispersion at this time. With a further increase in the mixing time(6—10 min), fillers in rubber tend to re-aggregate, leading to an increase in the mean agglomerate size and a decrease in dispersion, negatively impacting the dynamic and static properties of the rubber.

    Relaxation Dynamics of a Highly Stretched Single Polymer Chain in a Dilute Solution
    YAO Ning, WANG Haijun, LI Jiangtao, GU Fang, LIAO Qi
    2024, 45(4):  20240037.  doi:10.7503/cjcu20240037
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    For the relaxation of a highly stretched single polymer chain in dilute solutions of various solvent qualities, the relaxation dynamics was investigated through the methods of analytical theory and molecular dynamics(MD) simulation. To facilitate the comparison, the equilibrium and non-equilibrium routes were employed in the simulations, where the equilibrium route is performed by using the self-correlation function of related physical quantities. The reason for using the non-equilibrium route is that it is directly related to many practical processes, and the dynamic evolution of the scaling behavior between the relaxation time and normal modes can be present clearly. Consequently, it is found that at the initial stage of relaxation, some physical quantities would be influenced by the non-equilibrium initial state of the polymer chain, while after a certain time, the relaxation dynamics is consistent with that predicted the equilibrium state. Meanwhile, the two routes showed the same scaling behavior between the longest relaxation time and chain length. The non-equilibrium route is therefore helpful to investigate the whole relaxation process of a polymer chain, thereby giving more information of structure-property. It is expected that such an effort can provide some useful clues to pertinent topics.

    Synthesis of Furan-based Phosphaphenanthrene Flame Retardant and Its Application in Anti-flammable Epoxy Thermosets
    TANG Gang, TAO Yi, DENG Dan, ZHANG Dongxin, ZHANG Shihua, LIU Xiuyu, WU Qiang, SHEN Haifeng, SUN Junjie
    2024, 45(4):  20230494.  doi:10.7503/cjcu20230494
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    A novel bio-based flame retardant(Furan-2DOPO) was synthesized from 5-hydroxymethylfurfural, furfuramine, phosphorus oxychloride and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO). Its structure was characterized by Fourier transform infrared spectroscopy, proton- and phosphorus-nuclear magnetic resonance spectroscopy. A series of cured flame retarded epoxy products was obtained by modification of epoxy resin with Furan-2DOPO. The effects of the loading of Furan-2DOPO on the mechanical properties, thermal stability and flame retardant properties of the cured epoxy products were investigated. The results showed that when the addition amount of Furan-2DOPO was only 5%(mass fraction, phosphorus mass fraction was 0.47%), the oxygen index of the cured epoxy product reached 31.0%, and can pass the UL-94 V-0 test; compared with the unmodified epoxy resin, the peak heat release rate of the cured epoxy products containing 2.5%(mass fraction) and 5%(mass fraction) Furan-2DOPO was decreased by 31% and 35%, respectively. In addition, the tensile strength of the cured epoxy products containing 2.5% and 5% Furan-2DOPO was about 28% higher than that of the unmodified epoxy resin, respectively. The results of char analysis indicated that Furan-2DOPO possessed excellent catalytic charring performance, which was conducive to reducing the escape of combustible gases during combustion, so as to improve the flame retardant performance.

    Compatibility of Polyvinyl Chloride-Polyvinyl Alcohol and Structure and Properties of Their Composite Porous Membranes
    ZHU Jun, GUO Yue, WU Yang
    2024, 45(4):  20230479.  doi:10.7503/cjcu20230479
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    Polyvinyl chloride-polyvinyl alcohol(PVC-PVA) composite porous membranes were prepared by solution filming, the compatibility of PVC-PVA was analyzed from the perspective of mixing enthalpy and inter-molecular interactions. The pore morphology, hydrophilicity, filtration performance and mechanical properties of the composite porous membranes were analyzed by scanning electron microscopy(SEM), contact angle measurement and plate ultrafiltration membrane test, etc. The research results show that hydrogen bonds and dipole interactions could be formed among macromolecules in PVC-PVA composite system, the mixing enthalpy show a trend of first increasing and then decreasing with the increase of the mass fraction of PVA in polymers, and PVC-PVA is generally partially compatible. Compared with pure PVC membrane, the “finger like pore” feature of the cross-section of PVC-PVA composite membrane became weaker, while the “sponge pore” feature became apparent, and the pure water flux of the composite prous membrane was increased, the pollution resistance was improved, and the mechanical toughness was enhanced. When the mass fraction of PVA in polymers was 9%, the pure water flux of the composite membrane was about 4 times that of pure PVC membrane, the retention rate of PEG100000 was 80%, the strength was 3.5 MPa, and the elongation at break was 26%, the composite has a good application prospect in the field of water treatment.

    Synergistic Flame-retardant Epoxy Resin Using Quaternary Phosphate Naphthalene Sulfonate Ionic Liquid and Dimethyl Methylphosphonate
    ZHANG Lu, LIU Jie, LOU Shenghui, JIANG Hui, WANG Song, LI Sanxi, TANG Tao, ZHANG Ailing
    2024, 45(4):  20230467.  doi:10.7503/cjcu20230467
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    A novel room temperature ionic liquid of quaternary phosphate naphthalene sulfonate([TBP]NS) was synthesized. The structure of [TBP]NS was determined by Fourier transform infrared spectroscopy(FTIR) and nuclear magnetic resonance spectroscopy(1H NMR and 31P NMR). [TBP]NS was combined with dimethyl methylphosphonate(DMMP) to prepare flame-retardant epoxy resin. The flame-retardant results showed that when 6%(mass fraction) of [TBP]NS and 4%(mass fraction) of DMMP were added into epoxy resin(EP), the limiting oxygen index of the flame-retardant EP reached 31.2%, and EP/6%[TBP]NS/4%DMMP passed the UL-94 vertical combustion V-0 level. Compared with pure EP, the EP/6%[TBP]NS/4%DMMP showed a 59% reduction in peak heat release rate(PHRR), a 43% reduction in total heat release rate(THR), a 41% reduction in peak carbon monoxide release rate(PCOP), and a 97% increase in char yield. [TBP]NS and DMMP showed excellent synergistic flame retardancy in both the gaseous phase and the condensed phase, and good charring ability and heat reduction effect. In terms of mechanical properties, the tensile strength, elongation at break and bending strength of the EP/6%[TBP]NS/4%DMMP were all improved compared with those of the EP with DMMP alone.