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    10 June 2019, Volume 40 Issue 6
    Content
    Cover and Content of Chemical Journal of Chinese Universities Vol.40 No.6(2019)
    2019, 40(6):  0-0. 
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    Review
    Research Progress on Terahertz Stealth and Shielding Materials
    HUANG Zhiyu, CHEN Honghui, MA Wenle, HUANG Yi, ZHU Dan, CHEN Yongsheng
    2019, 40(6):  1103-1115.  doi:10.7503/cjcu20180627
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    The simulation methods on terahertz stealth and shielding performance were briefly introduced, and the research progress on terahertz stealth and shielding materials was mainly reviewed. In addition, the existing problems as well as prospects were also proposed.

    Articles
    Preparation, Characterization and Gas Adsorption Properties of Metal-Organic Aerogels
    LI Zhan,SHAN Xiaowen,YANG Pingping,GAO Zhuangzhuang,FANG Qianrong,XUE Ming,QIU Shilun
    2019, 40(6):  1116-1120.  doi:10.7503/cjcu20190102
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    A series of UiO-66 metal-organic frameworks(MOFs) with excellent stability was used to prepare metal-organic aerogels as a feasible way for the modeling of MOFs. The as-prepared UiO-66-based metal-organic aerogels(MOAs) possessed hierarchical pore structure and high surface area, which were very promising in gas adsorption and separation applications. In gas adsorption measurements, the amine modified UiO-66-NH2 aerogel exhibited outstanding adsorption capacity towards CO2 and high selectivity up to 18.3 towards CO2/CH4 mixture(molar ratio, 1∶1) calculated through ideal adsorbed solution theory.

    Inorganic Chemistry
    Synthesis of SnNb2O6 Nanoplates and Its Application for Danofloxacin Adsorption
    ZHAO Jie,SONG Qiang,GUO Xiao,WU Fei,TIAN Haochuan,LU Zhaowei
    2019, 40(6):  1121-1127.  doi:10.7503/cjcu20190005
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    A novel SnNb2O6 nano-adsorbent was prepared via hydrothermal method. The structure and morphology of the sample were characterized by X-ray powder diffraction(XRD), scanning electron microscopy(SEM) and Brunauer-Emmett-Teller(BET) techniques. Danofloxacin, as one of the third generation of quinolone antibiotics, was used as the adsorption target. The influencing factors experiment, adsorption kinetics experiment and isothermal adsorption experiment were designed to investigate the adsorption performance and adsorption mechanism of SnNb2O6 adsorbent. The results showed that the SnNb2O6 adsorbent has a layered monoclinic phase crystal structure with a specific surface area of 52.89 m2/g. In addition, the amount of adsorbent, adsorption temperature, pH value and adsorption time all have an effect on the adsorption efficiency. The adsorption process conforms to the Freundlich equation at 35 ℃ and the adsorption kinetics meets the Pseudo-second-order kinetic equation, suggesting liquid film diffusion is dominant factor in adsorption process. At optimal conditions of 35 ℃ and pH=6.02 with the dosage of 0.09 g, the adsorption efficiency is up to 93.1% in 30 min.

    Analytical Chemistry
    Dicyanostilbene-derived Two-photon Fluorescence Environment-sensitive Probe
    HUANG Chibao,PAN Qi,CHEN Huashi,LIANG Xing,LÜ Guoling
    2019, 40(6):  1128-1134.  doi:10.7503/cjcu20190006
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    A novel two-photon fluorescence environment-sensitive probe(SP) with the push-pull electronic architecture derived from dicyanostilbene was developed. This was a typical example of the combination of solvatochromism and molecular rotor properties. The maximum emission wavelengths of the probe SP increased significantly with the increase of the polarities of the solvents, which was attributed to the transformation of the excited state molecule into one or more torsional intramolecular charge transfer states(TICT). Polar solvents were more conducive to the stability of the charge separation state molecule. In the TICT state, the fluorescence quantum yield of the molecule was strongly dependent on the polarity, viscosity and temperature of the solvent. The probe SP showed a fairly wide range of solvent solvatochromism, the maximum emissiom wavelengths were 445 in cyclohexane and 641 nm in dimethyl sulfoxide, respectively, and the gap was 196 nm. The probe SP was able to be used for the detection of solvent polarity, viscosity and temperature, and the recognition of solvent species. The probe SP also had large two-photon absorption cross sections, the maximum two-photon absorption cross sections were 5560 in cyclohexane and 130 GM in N,N-dimethylformamide, respectively, and a super-large Stokes shift which was 232 nm. The probe was able to be used for the measurement and imaging of cell viscosity.

    Rapid Detection of Trace Organophosphorus Pesticides by Membrane Enrichment Combined with Membrane Image Colorimetric
    XIONG Qin,YANG Wuye,YANG Shaojie,LIU Jing,YANG Shihua,CHEN Wanchao,LI Long,DU Yiping
    2019, 40(6):  1135-1140.  doi:10.7503/cjcu20180799
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    A new method was developed for the rapid detection of organophosphorus pesticides based on smartphone and multi-channel membrane enrichment. According to the property that the activity of acetylcholinesterase was reduced by the specific inhibition of organophosphorus pesticides, indole acetate was used as a substrate which can be hydrolyzed by enzyme to form indigo. Indigo was enriched on a nylon membrane by the multi-channel membrane enrichment device with which analyte in standard solutions and sample solutions can be enriched on the same membrane at different positions. A mobile APP was developed to detect the membrane. Digital photographs of membrane were collected by the phone. With the APP, the influence of illumination and noise was eliminated and all samples enriched at different positions on the membrane could be identified automatically, the color signal of the samples were extracted, thus a standard curve of the color signal vs. concentration of the pesticide could be regressed. Limit of detection of trichlorfon was estimated being 0.030 mg/L. The content of trichlorfon in cucumber was analyzed with the developed method. The results showed that the recoveries were 95.8%—106.9% with relative standard deviations of 3.8%—5.4%. Using a smartphone but spectrometer, the proposed method is simple and applicable. Comparing with the method of GB/T 5009.100-2003, sensitivity and accuracy are improved significantly. The method showed potential applications in fast detection fields.

    Quantitative Determination of the Glycosylation Level for the Binding Proteins to High Density Lipoprotein by Mass Spectrometry
    WEI Wanghui,CHU Yanqiu,CHEN Ying,Gao Yanqiu,DING Chuanfan
    2019, 40(6):  1141-1149.  doi:10.7503/cjcu20180782
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    The protein content, site-specific glycosylation, and site occupancy of glycan and so on for serum amyloid A(SAA), α-1-antitrypsin(A1AT), α-2-HS-glycoprotein(A2HSG) and apolipoprotein C-Ⅲ(Apo C3) bound to high density lipoproteins(HDL) were investigated by mass spectrometry. Four kinds of trypsin digested protein standard samples were fragmented in liquid phase-quadrupole time-of-flight mass spectrometer. Some new glycosylation sites and new glycoforms were found by analyzing and matching fragment ions. For A2HSG, one O-glycosylation site and four glycoforms at that site were found, as well as 11 glycoforms at the original three sites. For Apo C3, 9 glycoforms at the original site were founded. Meanwhile, a unique peptide that used to quantify the protein were adjusted to make the quantification more accurate. Moreover, the multiple reaction monitor(MRM) behavior of peptides and glycopeptides in four proteins were studied and the site occupancy rate of each glycoform were recalculated. It is expected that our new findings in the process of exploration of site-specific glycosylation of HDL bound SAA, A1AT, A2HSG and Apo C3 will provide valuable informations in search of new HDL biomarks and will probably be practically applied in clinical detection of diseases related to HDL.

    Preparation and Enrichment Properties of Novel Magnetic Restricted Access Media-molecularly Imprinted Composites
    WU Shanshan,WEI Chanling,ZHAO Lijuan,TIAN Yang,WANG Xia,GONG Bolin
    2019, 40(6):  1150-1157.  doi:10.7503/cjcu20180772
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    The magnetic attapulgite(MATP) was preparrd by pyrolysis method. Then, using sulfadimethoxine(SDM) as template molecule, 4-vinylpyridine(4-VP) as functional monomer, the imprinted layer was coated on the surface of modified MATP via reverse atom transfer radical polymerization(RATRP), getting magnetic molecularly imprinted polymers(MATP-MIPs). Finally, novel magnetic restricted access media-molecularly imprinted composites(MATP-RAM-MIPs) was obtained by grafting hydrophilic monomer hydroxyethyl methacrylate(HEMA) onto the surface of MATP-MIPs. The polymer was characterized by means of Fourier transform infrared(FTIR) spectrum, scanning electron microscope(SEM), thermogravimetric analysis(TGA), vibrating sample magnetometer(VSM) and X-ray diffraction(XRD). The hydrophilicity of MATP-RAM-MIPs and the ability of exclusion of proteins were studied by the water contact angle and Coomassie brilliant blue G-250 method. The adsorption characters of MATP-RAM-MIPs on SDM were studied by adsorption isothermal and selectivity in detail, and MATP-RAM-MIPs were used as solid phase extraction packing to separate and enrichment of SAs from bovine samples. The spiked recoveries were 86.2%—100.6%, and the relative standard deviations(RSD) were 2.1%—4.2%, indicating that this material has application value in the pretreatment of complex samples.

    Highly Selective Topological Index of Chemical Bonds and Its Applications
    WU Ting,CHEN Mengyao,XIAO Kaixia,ZHOU Yanmei,ZHANG Qingyou
    2019, 40(6):  1158-1163.  doi:10.7503/cjcu20180759
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    On the basis of highly selective topological indices of molecules and atoms, a highly selective topological index of chemical bonds-bATID was suggested. More than 3 million chemical bonds in virtual and real data sets were individually used to test the uniqueness of bATID, and no degenerates, which indicates that bATID possesses strong identification ability of chemical bonds. Further, the bATID was applied to the identification of bonds of organic compounds, and satisfactory results were obtained. For example, the 90 chemical bonds of fullerene C60 were successfully identified by bATID as 30 of 6∶6 chemical bonds and 60 of 5∶6 chemical bonds. The research also indicates that the bond identification of bATID can be applied to the automatic identification of chiral centers and atomic permutation for the enumeration generation of automorphic group.

    Organic Chemistry
    Preparation, Structure and Pharmaceutical Analysis of Protamine-siRNA Complexes
    SHI Mai,JIANG Rui,CUI Xinxia,ZHANG Xin,SHEN Shigang,DING Liang,PAN Xuefeng
    2019, 40(6):  1164-1171.  doi:10.7503/cjcu20180833
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    Protamine-siRNA complexes of different morphologies were prepared by vortex mixing different mass ratios of protamine and siRNA at room temperature, which could be resolved by polyacrylamide gel electrophoresis with silver staining. The protamine-siRNA complexes were observed under atomic force and transmission electron microscopy, respectively. It was found that similarly shaped protamine-siRNA complexes could be formed by protamine with different siRNA molecules, indicated that the interaction between protamine and siRNA was independent on the base composition of siRNA. Moreover, the interactions between the protamine and the siRNA molecules were characterized by ionic probes, including Mg2+ etc. And the morphologies, the particle sizes as well as the structural properties of the protamine-siRNA complexes were further characterized using atomic force microscope, dynamic light scattering and transmission electron microscope, respectively. The results show that protamine formed toroid complexes and fibrous composites with siRNA molecules respectively in the light of the different mass ratios between protamine and siRNA. In the meantime, the phagocytosis and the pharmacodynamics of protamine-siRNA complexes of different morphologies were compared and measured using melanoma cells.

    Synthesis of 4-Hydroxyisoleucine Catalyzed by Recombinant Escherichia coli Expressing Fe(Ⅱ)/2-Ketoglutarate-dependent Dioxygenase
    ZHANG Wenli,NIE Yao,JING Xiaoran,XU Yan
    2019, 40(6):  1172-1177.  doi:10.7503/cjcu20180794
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    4-Hydroxyisoleucine(4-HIL) was synthesised using L-isoleucine(L-Ile) as substrate, the recombinant Escherichia coli BL21/pET28a-ido heterologously expressing Fe(Ⅱ)/2-ketoglutarate-dependent dioxygenase, and the whole cell as a catalyst. Based on the catalytic properties and conditions of L-Ile dioxygenase catalyzing isoleucine hydroxylation, the optimization of single factors included ferrous sulfate(FeSO4·7H2O), α-ketoglutaric acid(α-KG) and substrate concentration. As a result, the optimized yield of 190 mmol/L of 4-HIL was obtained in the 50 mmol/L trimthylolamine hydrochloride(Tris-HCl) buffer system comprising FeSO4·7H2O(2 g/L), with the molar ratio of substrate to α-KG molarity as 1∶1. Associated with the optimized conditions in shake flask level, the stirring speed and the cell concentration were further optimized at the reactor level, to achieve continuous regulation of isoleucine hydroxylation at high substrate concentration. Consequently, a whole-cell transformation system and process was established to produce 400 mmol/L 4-HIL, with the conditions of FeSO4·7H2O(2 g/L), molar concentration ratio of substrate and α-KG 1∶1, wet bacteria 50 g/L, and rotation speed 400 r/min.

    Selective Oxidation of Benzyl Alcohols Catalyzed by UiO-67-Sal-CuCl2 in Air
    QIAN Wenhao,HUANG Wei,CONG Yufeng,LI Fusheng
    2019, 40(6):  1178-1183.  doi:10.7503/cjcu20180767
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    Metal-organic-frameworks(MOFs) are a class of hybrid materials with unique porous structure. MOFs possess open pores of a permanent crystalline matrix, made of organic ligands and metal ions or clusters via coordination interactions. Permanently microporous MOFs materials have attracted considerable attention due to the large internal surface areas, uniform channels, thermal stability and other potential applications, such as gas separation and storage, catalysis, drug release and chemical sensing. The Zr-based MOF material(UiO-67-Sal) was functionalized through one-step hydrothermal synthesis, and the three copper(Ⅱ) salts were immobilized onto the UiO-67-salen. The three resulting Cu(Ⅱ)-UiO-67-Sal MOFs were evaluated for aerobic selective oxidation of a range of primary aromatic alcohols. The UiO-66-Sal-CuCl2 catalyst exhibited excellent activity toward the selective erobic oxidation of primary aromatic alcohols using oxygen molecular as the oxygen source. Furthermore, the UiO-66-Sal-CuCl2 catalyst showed a good recycle performance.

    Dynamic Biotransformation of Protopanaxadiol-ginsenosides and Preparation of Minor Ginsenosides C-K or F2
    XIAO Yongkun,LIU Chunying,YU Hongshan,YI Tea-Hoo,XU Longquan,SONG Jianguo,IM Wan-Teak,SUN Changkai,JIN Fengxie
    2019, 40(6):  1184-1192.  doi:10.7503/cjcu20180709
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    In order to efficiently produce high-bioactive minor ginsensoide C-K or F2, the protopanaxadiol(PPD) ginsenosides from American ginseng were converted by the enzyme from Aspergillus niger g.848 strain. The mass fractions of PPD ginsenosides were 49.6% Rb1, 25.9% Rd, 19.3% Rc and 5.23% Rb2, respectively. In fermentation, when the PPD-ginsenosides as a ginsenosidase-inducer, the 10%—15% ginsenosidase activity was increased than that of ginseng-extract ginsenosidase-inducer. The two enzymes were all the Ginsenosidase typ1-I. However, the enzyme by the ginsenosidase-inducer could hydrolyze almost PPD-ginsenosides into C-K, but the enzyme by ginseng extract-inducer hydrolyzed PPD-ginsenosides into F2, C-K, C-Mc and C-Y. When reacted for 1.5 h to 3 h, the main product was F2. When reacted for over 12 h, the main product was C-K. In the C-K preparation, 40 g of PPD-ginsenosides was reacted at 45 ℃ and pH=5.0 for 24 h to get 23 g product containing over 87%(mass fraction) C-K, the C-K molar yield was 85%. In the F2 preparation, 40 g PPD-ginsenosides was reacted at 45 ℃ and pH=5.0 for 2.5 h to get 26 g product containing 58%(mass fraction) of F2 and 27% of C-K, the molar yield was 50.4% for F2, and 29.5% for C-K. Therefore, according to biotransformation of the enzyme by PPD-ginsenosides-inducer, the 85% of C-K, or 50% of F2 was successfully prepared from PPD ginsenosides of American ginseng. The results are very usable for ginseng development.

    Physical Chemistry
    Vesiculation and Stability: Oligomer of Conjugated Linoleate Acids Prepared by High Internal Phase Self-emulsion Polymerization
    FAN Ye,LIU Tingting,FANG Yun,XIA Yongmei
    2019, 40(6):  1193-1200.  doi:10.7503/cjcu20190084
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    High internal phase O/W emulsion of conjugated linoleic acids(CLA) was prepared by self-emulsifying technology, and oligomer of CLA(oligo-CLA) was obtained by thermal self-emulsion polymerization(SEP) of the above emulsion. Furthermore, fatty acid vesicles(FAV) self-assemble by the oligo-CLA showing 10—30 nm diameter at pH=8.6—13 that was revealed by both transmission electron microscopy and dynamic light scattering, which has theoretical significance for FAV stable at a broader pH range. The experimental results show that free-surfactant emulsion polymerization was completed in the high internal phase emulsion of 75.3%(mass fraction) CLA according to the unique self-emulsification/thermal oligomerization strategy, achieving 33% total self-crosslinking degree and the target oligo-CLA with an average polymerization degree of 6, which is instructive for scaling up oligo-CLA and FAV preparation. The oligo-CLA has better low temperature solubility in comparison with CLA itself, and the FAV self-assembling by it has stronger resistance to acidic and calcium conditions and shows calcium responsive size-tunable features. Moreover, the hybrid vesicles of oligo-CLA with a small amount of Span 40 or AEO2 additives show even broader pH windows for vesiculation. Therefore the FAV self-assembling by oligo-CLA should have a wider application prospect in drug delivery systems, daily chemical products, and household detergents and personal care products.

    Effect of Aspect Ratio on Liquid Crystal Behavior of Ellipsoidal Particles
    XU Mingjie,SUN Yuwei,ZHU Youliang,FU Cuiliu,HUANG Yineng,LI Zhanwei,SUN Zhaoyan
    2019, 40(6):  1201-1206.  doi:10.7503/cjcu20190059
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    The Gay-Berne model and molecular dynamics simulation method was used to study the influences of aspect ratio on the liquid crystal behaviors of ellipsoidal particles, especially focusing on nematic and smectic phases. The results indicated that the ellipsoids with a relatively small aspect ratio favor the formation of nematic phases, while the ellipsoids with a relatively large aspect ratio prefer the formation of smectic phases. Furthermore, the formation processes of the nematic and smectic phases in detail were analyzed. The results provide theoretical guidance for designing different types of liquid crystals and understanding the formation mechanism of liquid crystal.

    Molybdenum Modified Nickel Phyllosilicates Catalyst for Maleic Anhydride Hydrogenation
    XIA Xiaoli,TAN Jingjing,WEI Caiyun,ZHAO Yongxiang
    2019, 40(6):  1207-1215.  doi:10.7503/cjcu20190022
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    A series of molybdenum-modified nickel phyllosilicates was synthesized by ammonia evaporation method. The effects of molybdenum content on the structure and catalytic performance of the catalyst for the liquid phase hydrogenation of maleic anhydride(MA) were investigated. The structure and morphology of the catalysts were characterized by N2 adsorption-desorption, XRD, FTIR, TEM, H2-TPR, NH3-TPD, Py-IR and in situ XPS. The results displayed that the introduction of molybdenum has a remarkable influence on the morphology of the catalysts and its catalytic properties. The reduction degree of the active metal Ni and the sites of Ni0 on the surface of the catalysts were increased with the addition of Mo. Meanwhile, the hydrogen spillover was generated during the Ni reduction process. Such overflowing active hydrogen have super reduction ability, which can promote partial of MoO3 to be reduced to MoOx species that possesses Lewis acid properties. Due to the synergistic effect between the surface Ni0 and the Lewis acid sites induced from partially reduced Ni(Niσ+) and MoOx, the catalytic performance of the catalyst was significantly improved for the hydrogenation of C≡C and C≡O groups in MA. The sample with the Mo doping content of 3% exhibits the highest activity. A 100% conversion of MA together with a γ-butyrolactone(GBL) selectivity of 27% was achieved within 3 h at 160 °C and the H2 pressure of 5 MPa.

    Preparation and Performance of Nano-porous Si/Graphite/C Composite Microspheres as Anode Material for Li-ion Batteries
    LIN Weiguo,SUN Weihang,QU Zongkai,FENG Xiaolei,RONG Junfeng,CHEN Xu,YANG Wensheng
    2019, 40(6):  1216-1221.  doi:10.7503/cjcu20180856
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    Porous Si was obtained from magnesiothermal reduction method using diatomite as the precursor, sand milling was carried out to prepare nano-porous Si(np-Si), After that, the np-Si was uniformly mixed with flake graphite and pitch by ball milling. Then np-Si/graphite/C composite microspheres were prepared by spray drying technology and calcined at high temperature. The structure and physicochemical properties of the composite microspheres were characterized. As anode material for Li-ion batteries, the results from electrochemical test reveal that the composite microspheres exhibit high reversible capacity(817 mA·h/g), excellent cycle stability(790 mA·h/g with 96.7% capacity retention after 100 cycles) and good rate performance. The superior electrochemical characteristics are mainly attributed to the hierarchical buffer structures composed of nanosized porous Si, graphite and pitch carbonized outer carbon, which effectively suppress the volume expansion of Si.

    Controllable Synthesis of Ti-Beta Zeolite and Efficiently Catalytic Epoxidation of Cyclohexene
    LIU Xinchao,ZHAO Yarong,YUAN Zhenyan,ZHOU Dan,LU Xinhuan,XIA Qinghua
    2019, 40(6):  1222-1228.  doi:10.7503/cjcu20180844
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    The construction of a green catalytic reaction system with characteristic of high efficiency for the synthesis of epoxycyclohexane by catalytic epoxidation of cyclohexene with H2O2 was focused. We succeeded in synthesizing Ti-Beta zeolites in the absence of Al by the dry-gel conversion method using tetraethylammonium hydroxide(TEAOH) as the structure directing agent with n(H2O)/n(Si) of about 1.5. We found that the crystallization, the uniformity of crystal and size of Ti-Beta were significantly affected by proper acidity and basicity, the amount of water and template dosage. Then, highly efficient Ti-Beta catalyst was prepared by calcination treatment of the raw powder. Under the optimal catalytic reaction conditions, the cyclohexene conversion of 33.5% and the epoxidation selectivity of 99.6% were achieved. The results indicate that Ti-Beta is an excellent heterogeneous catalyst.

    Molecular Dynamic of Various DNA Sequences Binding of Dithienylethenes
    SUN Haofan,ZHANG Lingyi,PATRICK Norman,ZHANG Weibing
    2019, 40(6):  1229-1235.  doi:10.7503/cjcu20180837
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    Binding modes between various DNA sequences and stereoisomeric rotamers of two dithienylethene derivatives(DTE1 and DTE2) representing photochromic switches were investigated in terms of molecular dynamics simulations and characterized by their binding energies. The result shows that minor groove binding(MiGB) is found to be the most robust binding mode between DNA and DTE(either DTE1 or DTE2). Due to steric hindrance, two DTE derivatives that are rotatable isomers exhibit distinct binding behaviors to DNA, and thus DNA has significant enantioselectivity for DTE derivatives. Moreover, the selectivity of the DTE derivative to the binding site of the DNA molecule is directly related to the base pair constitution, providing accurate theoretical guidance for precision medicine by chiral drugs based on this molecule.

    Droplet Condensation on Surfaces with Special Wettability
    LIN Yucai,PEI Wenle,SUN Ruoxuan,GAO Chunlei,CHEN Jipeng,ZHENG Yongmei
    2019, 40(6):  1236-1241.  doi:10.7503/cjcu20180820
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    The surfaces with micro/nano structures were fabricated by electrochemical corrosion and then boiling water treatment. Superhydrophobic surface was fabricated by chemical vapor deposition. Hydrophobic and hydrophilic surfaces were fabricated by coating surfaces with silicon oil and hydroxy-terminated silicon oil. Condensation on these surfaces (superhydrophilic, superhydrophobic, hydrophobic slippery and hydrophilic slippery) were investigated. Superhydrophilic surfaces show filmwise condensation. Both super hydrophobic and slippery surfaces show dropwise condensation. Superhydrophobic surfaces show out-of-plane jumping motion of the coalesced drops. Due to the wettability difference between the hydrophobic slippery surface and hydrophilic surface, fast droplet coalescence on hydrophilic slippery surfaces can effectively increase the droplet volume over time. The fog harvesting rates of different surfaces ranged in turn are hydrophilic slippery, hydrophobic slippery, superhydrophilic and superhydrophobic.

    In-situ Studies of Microstructure of CaF2-Al2O3-MgO Electroslag by Raman Spectroscopy and 27Al MAS NMR
    CAO Peiming,YOU Jinglin,ZHOU Candong,LU Liming,WANG Jian,WANG Min,DING Yani,XU Yandong
    2019, 40(6):  1242-1248.  doi:10.7503/cjcu20180795
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    The microstructure and Al coordination of crystalline, glassy and molten states of CaF2-Al2O3-MgO electroslag remelting slag were investigated by in-situ Raman spectroscopy and 27Al magic angle spinning nuclear magnetic resonance(MAS NMR). X-Ray diffraction was used to analyze phase of the crystal sample. Raman vibrational wavenumber and scattering activity of S-6530 crystal and melt were calculated based on density functional theory(DFT) and ab initio quantum chemical studies, respectively, and the major vibrational modes were assigned. The results showed that six-fold coordinated aluminum mainly exists in the S-6530 crystal, supplemented by a small amount of four or five-fold coordinated aluminum. During the heating process, the Al—O polyhedron of MgAl2O4 phase is transformed from [AlO6] to [AlO4] or [AlO5]. Al is present predominantly in [AlO4] tetrahedron in both S-6530 glass and melt, the proportion of [AlO4] is as high as 71.1%, compared with its crystalline state, the proportion of [AlO5] also increases to 28.6%. Based on quantum chemistry ab-initio calculation of the constructed molten cluster models, the [AlO4] configuration tends to be layered and frame structure dominated by Q3 and Q4 connections, and [AlO5] configuration remains isolated.

    Effects of Preparation Conditions on the Morphologies, Structures and Electrochemical Properties of MXene
    CHEN Yaoyan,ZHAO Xin,WANG Zhe,DONG Jie,ZHANG Qinghua
    2019, 40(6):  1249-1257.  doi:10.7503/cjcu20180783
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    Using Ti3AlC2 as precursor, multilayered Ti3C2Tx were prepared and intercalated in one process with LiF+HCl as etchant, and then single or few layers of two-dimensional(2D) MXene flakes were delaminated with following sonication. The studies were focused on the effects of etching and delamination conditions by tuning the ratios of etchant/Ti3AlC2(molar ratio) and the sonication time on the morphologies, structures and electrochemical properties of two dimensional crystal flakes of Ti3C2Tx. The results showed that selecting appropriate fabrication conditions is crucial to the structures and properties of MXene flakes. It is shown that the MXene obtained with 6 mol/L HCl, the LiF/Ti3AlC2 molar ratio of 7.5 and the sonication time of 1 h which named FMX7.5-6' displayed a small lattice constant and a large flake size up to 1 μm. It also had a high content of oxygen-containing functional groups and demonstrated the best electrochemical properties. At the current density of 0.5 A/g, it demonstrated a high specific capacity of 342 F/g and its capacity could reach 244 F/g at the current density of 20 A/g. The specific capacity could remain 87% of the original value after 10000 cycling test at the current density of 1 A/g, showing a good rate and stability performance.

    Effect of Nitrile Group Functionalized Organosilicon as Electrolyte Additive on Low-temperature Performance of LiFePO4 Battery
    ZHAO Xinyue,WANG Jinglun,YAN Xiaodan,ZHANG Lingzhi
    2019, 40(6):  1258-1264.  doi:10.7503/cjcu20180773
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    A nitrile group functionalized organosilicon compound, 3-(diethoxy-methyl-silanyl)-propionitrile(DESCN) was synthesized and its chemical structure and electrochemical window were characterized. The effects of DESCN on the low-temperature performance of LiFePO4 cell were investigated by charge-discharge cycling test, scanning electron microscopy(SEM), X-ray photoelectron spectroscopy(XPS) and electrochemical impedance spectroscopy(EIS) and so on. It is revealed that adding 2%DESCN could improve the low-temperature performance of LiFePO4 cell. At -20 ℃, the cell exhibits a high discharge capacity of 73 mA·h/g and are stable after 50 cycles. DESCN involved in the formation of stable solid electrolyte interface(SEI) film to inhibit electrolyte decomposition and decrease the battery resistance, which facilitate Li+ diffusion and electron transportation at electrode/electrolyte interface at low-temperature.

    Preparation of Amphiphilic Ti/ZSM-5 Zeolite and Its Catalytic Performance in Oxidative Desulfurization
    WANG Ying, SUN Chuanyin, WANG Runwei, ZHANG Zhendong, ZHANG Daming, ZHANG Zongtao, QIU Shilun
    2019, 40(6):  1265-1270.  doi:10.7503/cjcu20180770
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    Amphiphilic Ti/ZSM-5 zeolite(am-Ti/ZSM-5) was successfully prepared by asymmetric modification of Ti/ZSM-5 zeolite with diphenylsilane and aminopropyltriethoxysilane. The modification and post-treatment process did not destroy the framework structure of zeolite. The sample showed high catalytic activity in the oxidative desulfurization(ODS) of dibenzothiophene(DBT) using H2O2 as the oxidant and without adding the extractant. The complete removal of DBT from the simulated oil can be achieved within 35 min. These results indicate that the unique amphiphilic structure of am-Ti/ZSM-5 makes it have excellent catalytic performance in polar-nonpolar mixtures.

    Performance of Ru/graphene/carbon Nanotube Composites with Three-dimensional Network Structure as Positive Electrode Catalysts for Lithium Oxygen Batteries
    YIN Yanhong,LI Ke,DONG Hongyu,JIN Cheng,XIAO Xinglu,GAO Yicong,YANG Shuting
    2019, 40(6):  1271-1279.  doi:10.7503/cjcu2080706
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    Ru/graphene/carbon nanotube composites with three-dimensional network structure were prepared by physical impregnation and freeze drying. When the Ru content was 30%(mass fraction) and the heat treatment temperature was 500 ℃, the catalytic performance of the composite was optimal. When the composite was used as a cathode catalyst for lithium oxygen batteries, it exhibited excellent battery performance. When the first charge and discharge were performed at a current density of 50 mA/g, the discharge capacity density was about 5800 mA·h/g, and when the discharge capacity density was within 4000 mA·h/g, the polarization voltage was only was 0.9 V; when a constant-capacitance(500 mA·h/g) charge-discharge cycle was performed at a current density of 50 mA/g, the battery was stable for 12 cycles even when the polarization voltage was lower than 1.1 V. The three-dimensional network structure not only provided a transmission channel for O2 and Li+, but also increased the storage location of the discharge product Li2O2. The loading of the metal ruthenium nanoparticles not only increased the reactive site of the composite, but also promoted the decomposition of the discharge product Li2O2.

    Microwave-assisted Synthesis and Electrochemical Performance of Na-Doped Cathode Materials Li2-xNaxMnSiO4/C
    MA Dongwei,TIAN Runsai,LIU Zhenjiang,FENG Yuanyuan,DING Hongyu,FENG Jijun
    2019, 40(6):  1280-1287.  doi:10.7503/cjcu20180694
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    Li2-xNaxMnSiO4/C(x=0, 0.05, 0.09, 0.13) composite cathode materials were synthesized with microwave assisted sol-gel method. The crystal structure, morphology and electrochemical performance were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM), galvanostatic charge-discharge test, cyclic voltammetry(CV) and electrochemical impedance spectroscopy(EIS). The results indicate that the as-prepared materials can be well indexed to Pmn21 space group. The particles are fine with carbon layer coated uniformity and their size are evenly distributed in the range of 15—30 nm. With the synergistic effects of Na+ doping and microwave assisted in-situ carbon coating, the charge transfer resistance is reduced while the diffusion of Li+ is enhanced significantly, leading to excellent electrochemical performance. The Li1.91Na0.09MnSiO4/C exhibits an initial discharge capacity as high as 211 mA∙h/g at 0.1C and retained 80 mA∙h/g after 50 cycles. The reversible capacities at high rate currents are also improved obviously, with discharge capacities of 106 mA∙h/g and 53 mA∙h/g at 0.5C and 2.0C separately.

    Polymer Chemistry
    One-step Hydrothermal Synthesis of Copper Doped Carbon Dots and Their Application in White Light Devices
    DONG Xiangyang,NIU Xiaoqing,WEI Jishi,XIONG Huanming
    2019, 40(6):  1288-1292.  doi:10.7503/cjcu20190182
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    Copper doped carbon dots(Cu-CDs) were synthesized with aniline and copper acetate as raw materials. Through the optimization of experimental parameters, the optimal reaction time, reaction temperature and molar ratio of raw materials for Cu-CDs synthesis were 5 h, 210 ℃ and 1∶1, respectively. Comparing with the control group under the same conditions, it is found that the doping of Cu significantly improves the fluorescence intensity of CDs and achieves good multicolor luminescence performance. Cu-CDs can directly emit strong white light under 365 nm ultraviolet excitation. The white light emitting device is obtained with chromaticity coordinates of (0.337, 0.337) by further combining Cu-CDs with the ultraviolet light emitting diode(LED) chip. This method of preparing Cu-CDs materials in large quantity and its outstanding white light emitting performance have broaden the application of carbon dots in light emitting devices.

    Preparation of Lignin/silica Nanoparticle Based Microcapsules and Their Application in Self-healing Coatings
    LI Lan,QIAN Yong,YANG Dongjie,QIU Xueqing
    2019, 40(6):  1293-1300.  doi:10.7503/cjcu20190045
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    Phosphorylated lignin/silica nano composites(PAL/SiO2) were used as shell material to encapsulate active isophorone diisocyanate(IPDI) to prepare microcapsules(PAL/SiO2-IPDI). A small amount of polymeric methane diisocyanate(PMDI) with more reactivity was added to react with residual water to form polyurea, which could effectively increase the wall thickness of the microcapsules and improve the stability of the system. The effects of PAL/SiO2 nano composite content, water-oil ratio and shearing rate on the morphology, particle size and wall thickness of microcapsules were studied by optical microscopy(OM), scanning electron microscopy(SEM) and dynamic light scattering(DLS). The results show that the prepared PAL/SiO2-IPDI microcapsules were spherical with a wall thickness of 2.36—3.50 μm and an average diameter of 40.3—201.5 μm under optimum preparation conditions. Fourier transformed infrared spectroscopy(FTIR) and thermogravimetric analysis(TGA) revealed that the healing agent IPDI was successfully embedded as a core material in the microcapsules with a content of approximately 82.8%. The PAL/SiO2-IPDI microcapsules were blended with epoxy resin to prepare self-healing coatings. The anti-corrosion tests in the high salt concentration solution show that the epoxy resin coating containing 4%(mass fraction) PAL/SiO2-IPDI microcapsules could heal quickly after scratching, which significantly reduced the corrosion current and corrosion rate of the iron substrate. SEM images demonstrate that the pure epoxy coating had no sign of healing at the scratching area, while that in the self-healing epoxy coating was filled with cross-linking polymer. In addition, the nano indentation tests show that the hardness value of the epoxy coating increased from 249.99 MPa to 302.98 MPa after adding PAL/SiO2-IPDI microcapsules, and the elastic modulus was also improved.

    One-step Self-assembly/polymerization Fabrication and Biomedical Application of Carboplatin@Dextran Nanocarrier
    GAO Miaomiao,WANG Chenglong,DOU Hongjing,XU Guoxiong
    2019, 40(6):  1301-1309.  doi:10.7503/cjcu20180860
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    We introduced disulfide bond in the crosslinking points of the carboplatin@dextran to endow the reducing environmental sensitivity to the nanocarriers. Its structure, particle size and morphology of the nanocarrier were characterized by means of dynamic light scattering(DLS), 1H NMR and FTIR. The results showed that the size of the nanocarrier was (92±0.2) nm. In vitro drug release studies disclosed that the carboplatin inside the nanocarrier can be released for 80% in 72 h in a reducing environment. The cell uptake experiments showed that the nanocarriers loaded with carboplatin could efficiently enter the cell nuclei within 4 h. The half maximal inhibitory concentration(IC50) of the carboplatin@dextran nanocarrier was 25.32 μg/mL, which had similar cytotoxicity to the free carboplatin at the same concentration. The above results demonstrate that carboplatin@dextran nanocarrier prepared by the one-step method has a good biomedical application prospect.

    Non-enzymatic Glucose Sensor Based on the Electrospun Porous Foamy Copper Oxides Micro-nanofibers
    WANG Yongpeng,XU Zibo,LIU Mengzhu,ZHANG Haibo,JIANG Zhenhua
    2019, 40(6):  1310-1316.  doi:10.7503/cjcu20180854
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    A non-enzymatic glucose sensor using novel porous foamy CuO micro-nanofibers was fabricated through electrospinning and subsequent calcination. Scanning electron microscopy(SEM), Fourier transform infrared spectrum(FTIR) and X-ray differaction(XRD) techniques were used for the morphology and structural characterization of CuO nanostructures. CuO micro-nanofibers are highly dense, uniform, and exhibited good crystalline array structure. Most of all, the product presents a special rough foamy morphology with many pores, which help to enlarge the specific surface area thereby enhancing the activity of electrooxidation of glucose. The prepared CuO micro-nanofibers were subsequently used to modify a glassy carbon electrode and then detailed investigated for direct electrocatalytic oxidation of glucose through cyclic voltammetry and chronoamperometry. The results manifest that the modified electrode has a good sensitivity of 6.17 μA·L·mmol-1·cm-2 and a low detection limit of 65.3 μmol/L. Moreover, it exhibits a good antiinterference to ascorbic acid(AA), uric acid(UA) and ethanol as well. The improved performances were ascribed to the high surface-to-volume ratio and the special morphology. Therefore, it concluded that the porous foamy CuO micro-nanofibers can be a promising non-enzyme glucose sensor.

    Preparation of Fluorescence Polyurea Microspheres Through Precipitation Polymerization and Their Use for Fe3+ Determination
    GONG Minghui,YANG Shanshan,LI Shusheng,KUANG Rui,KONG Xiangzheng
    2019, 40(6):  1317-1323.  doi:10.7503/cjcu20180788
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    Uniform and fluorescent polyurea microspheres(FPU) were synthesized via precipitation polymerization of isophorone diisocyanate in water/acetone mixture, bonding different amount amino-functionalized 1,8-naphthalimide(AABD) as fluorescent chromorephore. The chemical structure of AABD was confirmed by 1H NMR and FTIR spectra. The AABD content in FPU was investigated by UV-Vis spectroscopy, and the enhanced properties of FPU was characterized by fluorescent spectroscopy. The results showed that, the uniform FPU microspheres of about 5 μm in diameter exhibited considerable green fluorescence emission at 522 nm when they were excited at 420 nm, and the fluorescence intensity was significant enhacced in comparsion with pure AABD in water or FPU dissolved in N-methyl pyrrolidone at the same concentration of AABD units. A linear decrease in fluorescence intensity of FPU was observed with increased Fe3+ concentration changed from 10-4 mol/L to 10-3 mol/L. This provides a potential application for AABD-containing FPU for Fe3+ determination in aqueous systems.

    Synthesis of Methylene-bridged Binuclear Metallocene Complexes and Application for Propylene Syndiospecific Polymerization
    SHAO Lu,LIANG Chunchao,XU Sheng,MI Puke,WANG Tinglan,YI Jianjun
    2019, 40(6):  1324-1332.  doi:10.7503/cjcu20180781
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    In order to investigate the differences between binuclear metallocene catalysts and mononuclear catalysts for propylene syndiotactic polymerization, binuclear metallocene complexes [μ,μ-(CH2)3]·{[C(H)(η5-C5H4)(η5-C13H8)](MCl2)}2[M=Zr or Ti](4, 5), and [μ,μ-(CH2)3]·{[C(H)(η5-C5H4)·(η5-C9H6)](MCl2)}2[M=Zr or Ti](6, 7) were synthesized and characterized by 1H NMR, 13C NMR, mass spectra and elemental analysis. When combined with methylaluminoxane(MAO), these metallocene complexes shown high catalytic activity for the polymerization of ethylene and propylene, the activity of polyethylene(PE) reaches up to 7.5×106 g PE/(mol Zr·h)(complex 6) and 10×105 g sPP/(mol Zr·h)(complex 4) for polypropylene(PP). The syndiotacticity index(SI) of polypropylene(sPP) by complex 4 was more than 90%. It is found that, under the same conditions, binuclear complexes’ catalytic activity, Mw(>100000) and molecular weight distribution(MWD>2.5) are higher than that of corresponding mononuclear metallocene complexes(Mw<70000, MWD≤2), which suggests that there are cooperation effect in binuclear system.

    Effect and Mechanism of Rare Earth Trifluoromethanesulfonate on the Thermal Stability of Polypropylene
    RAN Shiya,SHEN Haifeng,LI Xiaonan,WANG Zilu,GUO Zhenghong,FANG Zhengping
    2019, 40(6):  1333-1340.  doi:10.7503/cjcu20180727
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    The thermal degradation of polypropylene(PP) was a free radical chain reaction, in other words, free radicals were the primary cause of combustion and degradation. Rare earth trifluoromethanesulfonate [Yb(OTf)3 and La(OTf)3] can interfere degradation process of PP via capturing the free radicals, thus effectively improving the thermal stability of PP. PP composites filled with two kinds of rare earth trifluoromethanesulfonates were prepared via melt blending utilizing the free-radical trapping ability of Yb(OTf)3 and La(OTf)3 in this paper. The thermal-stability of PP was tested by thermogravimetric analysis(TGA), differential scanning calorimetry(DSC) and thermogravimetric analysis coupled to Fourier transform infrared spectroscopy(TGA-FTIR). The results showed that Yb(OTf)3 and La(OTf)3 could improve the thermal-stability of PP dramatically. Simply when the addition of Yb(OTf)3 was 1%(mass fraction), the onset degradation temperature of PP was increased from 275 ℃ to 305 ℃, the temperature corresponding to the maximum rate of mass loss increased from 384 ℃ to 405 ℃, the oxidative induction time at 160 ℃ extended from 12.1 min to 43.0 min, and the enthalpy reduced from 1907 J/g to 483 J/g, respectively. Moreover, the onset degradation temperature, the maximum rate of mass loss, the oxidative induction time at 160 ℃ and the enthalpy of PP filled with 1%(mass fraction) La(OTf)3 were 300 ℃, 409 ℃, 18.6 min and 633 J/g, respectively. The effect of La(OTf)3 on the thermal stability of PP was weaker than that of Yb(OTf)3. We tried to explain these differences and then propose the possible mechanism. Due to the combined action of anions and cations, Yb(OTf)3 and La(OTf)3 could improve the thermal stability of PP. For La(OTf)3, the free radical trapping ability of trifluoromethanesulfonate and the coordination ability of rare earth ions played a major role. For Yb(OTf)3, in addition to the above reasons, the high reactivity of rare earth ions also played a key role.