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10 March 2019, Volume 40 Issue 3

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Cover and Content of Chemical Journal of Chinese Universities Vol.40 No.3(2019)

2019, 40(3):  0-0. 

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Inorganic Chemistry

Synthesis of Novel Cd(Ⅱ) Metal-organic Framework for Highly Selective Detection of p-Nitroaniline^†

FU Linjie,LUO Ran,WANG Shuhua,ZHANG Ning,CHEN Chao

2019, 40(3):  419-424.  doi:10.7503/cjcu20180579

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1,3,5-Tri(1H-benzo[d]imidazol-2-yl) benzene(TBB) and(2,5-dihydroxyterephthalic acid)(H₂dhtp) were used as linear ligands and Cd(Ⅱ) was used as the central node to construct a new type of chiral 3D metal-organic framework materials Cd(TBB)(dhtp)(1). The strong fluorescence emission property of complex 1 and the π-π interaction of the TBB ligand made it possible to detect nitro compounds and other pollutants by fluorescence. A further study showed that 4-nitroaniline had a high quenching ability for complex 1 and the limit of detection could be as low as 0.145 mg/L, indicating that complex 1 could be used as a highly efficient and highly selective detection probe for p-nitroaniline.



Degradation of Organic Dyes over Regenerative Fe₃O₄/CuFeS₂/Biomass Composite Column^†

ZHANG Jubo,SUN Xiaohan,GAO Qiaojiao,WANG Haixin,LIANG Daxin,LIU Zhiming,HAN Guangting,JIANG Wei

2019, 40(3):  425-430.  doi:10.7503/cjcu20180340

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Monodispersed Fe₃O₄ nanospheres with diameters of (200±0.5) nm and CuFeS₂ nanocrystals with diameters of (6.5±0.5) nm were mixed with biomass wastes to prepare Fe₃O₄/CuFeS₂/biomass composite degradation column. The composite degradation column can effectively degradate organic dyes[methylene blue(MB) and rhodamine B(RhB)] aqueous solutions with degradation rates over 90%. Compared with other Fenton systems, Cu⁺ in CuFeS₂ enormously contributes to the Fenton process. At the same time, the magne-tism of the sample can make it easy to recover. More importantly, the degradation rates after regeneration can remain over 90%. Besides, the composite can make full use of biomass wastes.



Analytical Chemistry

Simultaneous Determination of Uric Acid, Xanthine and Hypoxanthine Based on Polyimidazole/Carbon Nitride Novel Nanocomposite^†

WANG Cun,MENG Li,HUI Junmin

2019, 40(3):  431-438.  doi:10.7503/cjcu20180717

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Two dimensional(2D) sheet-like structure of carbon nitride(g-C₃N₄) nanosheets containing winkles were synthesized, which were analogous to the crumpled graphene. At the same time, overoxidized polyimidazole(PImox)/g-C₃N₄ modified electrode(PImox/g-C₃N₄/GCE) was prepared by electrodeposition and oxidation at higher potentials. The composite materials were characterized by scanning electronmicroscopy(SEM) and X-ray diffractometry(XRD). The electrochemical behaviors of uric acid(UA), xanthine(XA) and hypoxanthine(HX) at the PImox/g-C₃N₄/GCE were investigated using cyclic voltammetry(CV) and differential pulse voltammetry(DPV). The calibration curves for UA, XA and HX were obtained over the ranges of 2.0—216.0, 5.0—542.0 and 5.0—778.0 μmol/L with the detection limits of 0.17, 0.30 and 0.30 μmol/L, respectively. PImox/g-C3N4/GCE has lower detection limits and wider linear range for simultaneous detection of UA, XA and HX. In addition, the modified electrode was applied to detect UA, XA and HX in real samples using standard addition method with satisfactory results. The recovery rates of the samples ranged between 98.4% and 105.2%.



Preparation of Thrombin Aptasensor Based on the Metal-organic Framework Fe-MIL-88N{{\mathrm{H}}_2}^{†}

LI Delei,GU Mengqiao,WANG Min,CHI Kuanneng,ZHANG Xi,DENG Yan,MA Yuchan,HU Rong,YANG Yunhui

2019, 40(3):  439-447.  doi:10.7503/cjcu20180563

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A sandwich-type aptasensor based on the metal-organic framework Fe-MIL-88NH₂ for the rapid detection of thrombin was developed. Amino-functionalized metal-organic framework(Fe-MOFs), Fe-MIL-88NH₂, was used as a label, which was covalently cross linked with amino-modified thrombin aptamer Ⅱ through glutaraldehyde. Gold nanoparticle modified covalent organic frameworks(Au NPs@COF-LZU-8) with high electronic conductivity was employed as the substrate to immobilize thiolated thrombin aptamer Ⅰ(TBAⅠ). After thrombin binds specifically with TBAⅠ, it combines with Fe-MIL-88NH₂ labeled thrombin aptamer Ⅱ. Then, iron ions(Fe³⁺) from Fe-MIL-88NH₂ were directly detected without acid dissolution and preconcentration. Under the optimized experimental conditions, the current response of Fe³⁺ in Fe-MIL-88NH₂ was directly proportional to the concentration of thrombin in the range of 0.5—200 ng/mL, with a linear correlation coefficient of 0.987 and a detection limit of 0.167 ng/mL. In this strategy, the detecting steps were greatly simplified. This article expands the application range of MOFs.



Preparation of Gold-modified Magnetic Graphene-based Molecularly Imprinted Composites and Electrochemical Sensing Detection of Dinbutyl Phthalate in Water^†

LI Ying, KANG Junjun, ZHAO Xueru, XU Wenkai, QI Qi

2019, 40(3):  448-456.  doi:10.7503/cjcu20180521

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Gold-modified magnetic graphene(Au@Fe₃O₄@RGO) was used as a carrier to select gold-modified magnetic properties and using surface molecular imprinting technique to select dinbutyl phthalate(DBP) as a template molecule in water environment. Graphene-based molecularly imprinted composite membrane(Au@Fe₃O₄@RGO-MIP) was prepared and characterized by means of transmission electron microscopy(TEM), X-ray diffraction(XRD) and Fourier transform infrared spectroscopy(FTIR). Au@Fe₃O₄@RGO-MIP was used as the sensitive material for sensor identification components. The performance of molecularly imprinted electrochemical sensors was analyzed by cyclic voltammetry(CV), electrochemical impedance spectroscopy(EIS) and differential pulse(DPV). The results show that the equilibrium time of the molecularly imprinted electrochemical sensor for dinbutyl phthalate in water environment is 6 min. In the concentration range of 0.01—0.1 μmol/L, there is a good linear relationship between DBP concentration and response current. The minimum detection limit is 0.3049 nmol/L(S/N=3).



Three New Phenolic Compounds from Salacia cochinchinensis Lour and Their α-Glucosidase Inhibitory Activities^†

ZHANG Juanrong,YOU Huimei,JING Yuxing,ZHAO Jiaowen,WANG Wei,LIU Wenxing,ZHOU Min,JIANG Zhiyong

2019, 40(3):  456-461.  doi:10.7503/cjcu20180622

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Five compounds were isolated from the stems and leaves of Salacia cochinchinensis Lour. By comprehensive spectroscopic analyses including mass spectroscopy(MS), infrared radiation(IR), 1D and 2D nuclear magnetic resonance(NMR) [heteronuclear single quantum coherence(HSQC), heteronuclear multiple bond correlation(HMBC), ¹H-¹H chemical-shift correlation spectroscopy(¹H-¹H COSY) and rotating frame overhauser effect spectroscopy(ROESY)], their structures were elucidated as Salaciacochinoside A(1), 5'-O-3,4,5-trimethoxybenzoyl-β-D-apiofuranoside(2), 5-methoxy-anticerol A(3), 21α,30-dihydroxy-D∶A-friedooleanan-3-one(4) and 21α,26-dihydroxyfriedelan-3-one(5), respectively. Compounds 1—3 were new compounds. All the compounds were assayed for the anti-diabetic activities. Compounds 1 and 3 exhibited remarkable bioactivity, inhibiting α-glucosidase with IC₅₀ values of 0.32 and 0.59 μmol/L, respectively. Compounds 2, 4 and 5 showed none anti-diabetic activity in current experiment.



Organic Chemistry

Carbonate Handle Modified Wang Resin and Its Function^†

ZHANG Ye,WU Weihui,ZONG Liang,DONG Junjun

2019, 40(3):  462-467.  doi:10.7503/cjcu20180548

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Because of the carbonate structure is removed by nucleophilic agents easily, methyl chloroformate was used to modify Wang resin, and the condensation efficiency of modified Wang resin with the first amino acid was studied. The results showed the condensation efficiency of the modified resin to 20 kinds of Fmoc amino acids could run up to 70%. In order to increase the condensation efficiency of the modified resin with the Fmoc amino acids achieving larger side chain groups, the degree of resin substitution was reduced and the reaction time was prolonged. In order to prove the protected side chain group would not be damaged under cleavage conditions of the modified Wang resin, three model peptides were resigned and synthesized, and cleaved by 3-pyridinecarboxaldehyde sulfonium salt. The results showed that the peptides with side chain fully protected could be obtained by using the modified Wang resin, and could also be preliminary applied to the synthesis of long-chain peptides.



Anti-glioma Active Compounds and Their Nanomicelles Preparation of the Root of Actinidiaeriantha Benth^†

TANG Lin,JIANG Zhenqi,LI Juan,WU Aiguo

2019, 40(3):  468-472.  doi:10.7503/cjcu20180507

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Actinidiaeriantha Benth was extracted by ethyl acetate, n-butyl alcohol and water, and three fractions were obtained. The in vitro cell experiments showed that ethyl acetate was the anti-glioma active fraction of the root of Actinidiaeriantha Benth. The high performance liquid chromatographic fingerprint confirmed that main compound of ethyl acetate fraction was 2α,3α,24-trihydroxyurs-12-en-28-oic acid, and it could significantly inhibit the glioma cell activity. The prepared 2α,3α,24-trihydroxyurs-12-en-28-oic acid loaded nanomicelles was with high loading efficiency of 64.7%, average diameter of 20 nm with polydispersity index(PDI) of 0.246 and ζ potential of -5.7 mV. Further cell experiment demonstrated the 2α,3α,24-trihydroxyurs-12-en-28-oic acid loaded nanomicelles through solvent evaporation with better inhibitory effects on the glioma cells than free one. Taken together, the ethyl acetate fractions from the root of Actinidiaeriantha Benth were confirmed with the anti-glioma activity, and 2α,3α,24-trihydroxyurs-12-en-28-oic acid was the main active compound. The prepared 2α,3α,24-trihydroxyurs-12-en-28-oic acid loaded nanomicelles was with good water dispersity and anti-glioma activity, providing solid experimental base for the application of the root of Actinidiaeriantha Benth in glioma therapy.



Physical Chemistry

Hydrogen Storage Capacity of the Alkaline Earth Metal Mg Exohedral Doped Boron Cage B₄₀M{{\mathrm{g}}_6}^{†}

ZHOU Xiaofeng,ZHOU Yanbing,TANG Chunmei

2019, 40(3):  473-480.  doi:10.7503/cjcu20180780

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The density functional theory(DFT) was used to study the hydrogen storage capacity of alkaline earth metal Mg exohedral doped B₄₀ cage structure. There are two B₆ hexagon rings and four B₇ heptagon rings in the B₄₀ cage. The clustering of the Mg atoms on the surface of the B₄₀ cage can be effectively avoided, which should be benefit for the further hydrogen storage. The average adsorption energy of H₂ molecules is intermediate between physical adsorption and chemisorption. The hydrogen gravimetric density of B₄₀Mg₆ is 7.60%(mass fraction), which far exceed the target of 5.5%(mass fraction) by the year 2017 specified by the US Department of Energy. The hydrogen adsorbed structure tends to desorb hydrogen under the near-ambient conditions. Therefore, the Mg atom exohedral doped B₄₀ cage has better hydrogen storage capacity than Mg alloy. This research can provide a very important theoretical basis for the development of hydrogen storage materials.



Effect of Potassium Stannate on the Deposition/Dissolution Behavior of Zinc Anode for Zinc-nickel Single-flow Battery^†

YAO Shouguang,CHEN Yong,CHENG Jie,SHEN Yaju,DING Dapei,YANG Yusheng

2019, 40(3):  481-488.  doi:10.7503/cjcu20180652

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The effect of potassium stannate additive on the deposition/dissolution behavior of zinc anode in flowing high concentration potassium zincate solution was studied. Cyclic voltammetry results show that when the scanning speed is 1 mV/s, the cathode branch deposits earlier with the increase of potassium stannate concentration, that is, the co-deposition of tin and zinc leads to the gradual decrease of dissolution peak with the increase of potassium stannate concentration. With the increase of scanning speed, the law becomes less obvious. SEM analysis shows that the addition of potassium stannate to the base solution is beneficial to seed production and grain growth. EDS tests show that the deposit from potassium stannate solution containing potassium stannate do contain zinc and tin. The self-discharge test shows that the self-discharge phenomenon is improved obviously after adding potassium stannate to the basic electrolyte. The Coulomb efficiency of the battery with 0.1 mol/L potassium stannate is increased from 60.0% of the basic solution to 81.1% after 12 h static charge. Therefore, the addition of potassium stannate in high concentration potassium zincate solution can benefit the production of seed and the growth of grain, produce compact small grains, make the deposit surface smoother and more compact, slow down the self-dissolution of zinc to a certain extent, and thus inhibiting the self-discharge effect.



Synthesis and Photocatalytic Performance of CdS/CuS Core-shell Nanocomposites^†

ZHANG Kejie,LI Yu,XIA Yuan,HAN Shuo,CAO Jing,WANG Hanyang,LUO Wentao,ZHOU Zhiping

2019, 40(3):  489-498.  doi:10.7503/cjcu20180596

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Four CdS/CuS core-shell nanocomposite samples with different molar ratios of CdS to CuS were synthesized via liquid-phase thermal decomposition and ion adsorption method under different crystallization time of CdS, using cadmium acetate, 2-mercaptobenzothiazole, sodium sulfide and cupric chloride as the raw materials. The experimental results indicated that the samples were spherical nucleus-like structures and their particle size was controllable with the crystallization time of CdS. The degradation efficiencies of rhodamine B(RhB) and methylene blue(MB) both reached about 99% when the molar ratio of CdS to CuS was 4∶1 and the crystallization time of CdS was 10 min. The method of ion adsorption makes CuS fully coat on the surface of CdS, forming effective core-shell structure and obviously improving the photocatalytic performance of CdS.



Preparation and Electrochemical Energy Storage Performance of One Dimensional Orderly Polyaniline Nanowires Array^†

LIU Ben,ZHANG Xingying,CHEN Shaoyun,HU Chenglong

2019, 40(3):  498-507.  doi:10.7503/cjcu20180590

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One dimensional orderly polyaniline(PANI) nanowires array were prepared on conducting substrate by using a galvanostatic current method. The effects of preparation factors, including concentration of aniline(0.01—0.3 mol/L), working current density(0.01—0.13 mA/cm²) and kinds of protonic acid(1 mol/L H₂SO₄, HCl, HNO₃ and p-TSA), on the morphology of the as-prepared PANI nanowires were investigated. It was found that the best morphology of PANI nanowires array could be obtained when the concentration of aniline was 0.1 mol/L and the working current density was 0.03 mA/cm². Also, the PANI with uniform nanowires array structure could not be formed when HCl, HNO₃ and p-TSA acted as supporting liquid. The as-prepared PANI nanowire arrays had narrow diameters and were oriented perpendicularly to the FTO, which was beneficial to the ion diffusion when being used as the supercapacitor electrode. The highest specific capacitance of PANI nanowire arrays was measured as 560 F/g at a charge-discharge current density of 1 A/g, and the PANI nanowire arrays also exhibited good capability and cycling stability with capacitance retentions of 89% after 1000 cycles, which is superior or close to some individual PANI nanostructures and PANI composite materials.



Preparation of Magnetically Recyclable Fluorinated Graphene and Its Demulsification Performance for Emulsified Oily Wastewater^†

XU Haiyan,REN Sili,JIA Weihong,WANG Jinqing

2019, 40(3):  508-517.  doi:10.7503/cjcu20180559

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Fluorinated graphene(FG) was firstly reduced by hydrazine hydrate to form the hydrophilic FG(HFG), and then magnetic Fe₃O₄ nanoparticles were further grafted onto the surface of HFG to synthesize HFG-Fe₃O₄ composite. The morphology, structure and chemical property of the samples were characterized by TEM, SEM, FTIR, XRD and XPS. In addition, the demulsification performance of HFG-Fe₃O₄ for oily wastewater was investigated and some affecting factors were discussed in detail. Moreover, the demulsification mechanism of HFG-Fe₃O₄ was proposed as well. The results show that the HFG-Fe₃O₄ is one kind of two-dimensional sheet-like material with Fe₃O₄ nanoparticles being uniformly distributed on its surface. The HFG-Fe₃O₄ has good demulsification performance on acidic and neutral oily wastewater, and its optimum dosage is 600 mg/L. Under the acidic and neutral conditions, the electrostatic attraction between HFG-Fe₃O₄ and the oily wastewater, as well as the π-π interaction between HFG-Fe₃O₄ and asphaltenes are the main forces promoting the oil separation from oily wastewater. However, the electrostatic repulsion between HFG-Fe₃O₄ and oily wastewater increases drastically under the alkaline condition, and ultimately results in the reduction of demulsification efficiency. What’s more, HFG-Fe₃O₄ still has excellent demulsification performance after 4 cycles, suggesting it has superior recyclability.



Electronic Structures and Optical Properties of Cu-based Semiconductors with Chalcopyrite-type Structure^†

ZHOU Hegen,JIN Hua,GUO Huirui,LIN Jing,ZHANG Yongfan

2019, 40(3):  518-527.  doi:10.7503/cjcu20180550

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The density functional theory(DFT) based on the pseudo-potential plane wave basis was employed to investigate the geometries, electronic structures, linear and second-order nonlinear optical properties of the CuXY₂(X=Ga, In; Y=S, Se, Te) crystals with chalcopyrite structure. The results indicate that these compounds are semiconductors with a direct gap and have similar band structures. The static dielectric constants, the refractive indices and the second harmonic generation(SHG) coefficients(d₃₆) of these compounds increase in the sequence of S→Se→Te for the same X atom. Among the occupied bands, those states near the top of the valence band contribute mostly to the SHG effect, which are dominated by the components of C{{\mathrm{u}}_3}_d orbitals and the valence p orbitals of Y atom. While for the unoccupied bands, the bands mainly derived from valence p orbitals of X atoms have obvious influences on the SHG coefficient. Among these six crystals, CuInSe₂ has high photoconductivity and better absorption of sunlight. In addition, CuGaS₂ and CuGaSe₂ crystal have potential applications in the second-order nonlinear optical fields based on their birefringences and SHG strengths.



Nano-SnO₂ as Highly Efficient Catalyst for Epoxidation of Cyclic Olefins with Aqueous H₂{{\mathrm{O}}_2}^{†}

LU Xinhuan,TAO Peipei,HUANG Fengfeng,ZHANG Xianggui,LIN Zhicheng,PAN Haijun,ZHANG Haifu,ZHOU Dan,XIA Qinghua

2019, 40(3):  528-535.  doi:10.7503/cjcu20180534

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A green catalytic reaction system with characteristic of high efficiency for the synthesis of epoxides by catalytic epoxidation of functionalized olefins with hydrogen peroxide was constructed. SnO₂ nanoparticles were prepared by hydrothermal synthesis method and calcined at 320 ℃. Subsequently, all catalysts were characterized by X-ray diffraction(XRD), UV-Vis diffuse reflectance spectroscopy(UV-Vis), Fourier transform infrared spectroscopy(FTIR), scanning electron microscopy(SEM) and transmission electron microscopy(TEM). Then, these catalysts were used to catalyze the epoxidation of various functionalized olefins, including cyclic olefins, styrene and linear olefins, using H₂O₂ aqueous solutions as oxidants, with high conversion for olefins and high selectivity to epoxides. Under similar reaction conditions, thus-synthesized nano-SnO₂-170 catalyst was found to be the most active one in the epoxidation of 1-methyl cyclohexene with H₂O₂, for which 100% of conversion and 100% selectivity were achieved within 2 h.



Preparation of TiO₂/CNTs Composite Coated Separator and Its Application in Li-S Battery^†

GUAN Yibiao,LI Wanlong,XIE Xiaoyi,QU Wei,SHEN Jinran,FU Kai,GUO Cuijing,ZHOU Shuqin,FAN Hongjia,CHU Yongjin,CHEN Renjie

2019, 40(3):  536-541.  doi:10.7503/cjcu20180514

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Porous TiO₂ was prepared with metal-organic framework MIL-125(Ti) as template, and CNTs were introduced to form the three-dimensional conductive TiO₂/CNTs composite. The TiO₂/CNTs composite was coated on one side of the separator and applied in lithium-sulfur battery. The morphology and elemental composition of TiO₂ were characterized by transmission electron microscopy(TEM), scanning electron microscopy(SEM) and X-ray photoelectron spectroscopy(XPS). The CNTs/S cathodes with TiO₂/CNTs composite coated separator deliver a high initial discharge capacity of 1051.1 mA·h/g and still retain a capacity of 904.8 mA·h/g after 150 cycles at 0.5C. Even at 1C, the capacity is still up to 1036.9 mA·h/g, and a high capacity of 763.0 mA·h/g is retained after 250 cycles, showing good rate performance.



Ultra-low Pt Loading Cathodic Catalyst Layer Prepared on Textured Gas Diffusion Layer by Magnetron Sputtering Method for Hydrogen-oxygen Fuel Cells^†

LIU Jiaming,FU Kailin,ZHANG Ze,GUO Wei,PAN Mu

2019, 40(3):  542-547.  doi:10.7503/cjcu20180491

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Ultra-low loading of Pt was deposited on the textured gas diffusion layer(GDL) by magnetron sputtering method to prepare cathodic catalyst layer for hydrogen-oxygen proton exchange membrane fuel cells(PEMFCs). The characterization of GDL before and after Pt-loading was carried out using scanning electron microscope(SEM), profilometer and X-ray diffractometer(XRD). The chemical states of sputter deposited Pt were investigated by X-ray photoelectron spectroscopy(XPS). The performance of membrane electrode asembly(MEA) was tested by fuel cell station. The results showed that the Pt deposited on the GDL was controllable and evenly distributed. The surface area of Pt deposited on the textured GDL was larger than that deposited on the commercial GDL. The fuel cell performance indicated that the Pt deposited on the textured GDL with the loading of 0.04 mg/cm² exhibited the maximum mass specific power of 26.25 kW/g Pt, which was higher than that of the Pt deposited on the commercial GDL(17.76 kW/g Pt). In addition, the maximum mass specific power of commercial Pt/C was 24.00 kW/g Pt.



Polymer Chemistry

Self-assembled Azo Molecular Glass Microspheres with Rapid Photoinduced Deformation^†

TANG Bo,HUANG Hao,WU Bing,LI Xu,WANG Xiaogong

2019, 40(3):  548-554.  doi:10.7503/cjcu20180679

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Azo molecular glass microspheres with photoinduced deformation properties have attracted attention for fabricating anisotropic particles and other specific-shaped particles. In this work, we investigated the self-assembly of an azo molecular glass(IAC-4) material in tetrahydrofuran/water(THF/H₂O) mixed solvents to form the colloidal spheres with uniform sizes in the dispersions as well as photoinduced deformation behavior of the formed IAC-4 microspheres. The intermediate states of self-assemblies were investigated via dynamic light scattering(DLS). The results showed that as the water content increased, the hydrodynamic radius(R_h) tended to increase to reach the maximum and then decreased gradually. The relationship between the critical water content(cwc) and initial concentration of IAC-4 in THF was proved to be consistent with the solubility of a solid solute in the binary mixed solvents, which indicated that IAC-4 underwent the transition from unsaturated state to a saturated state in the mixed solvents as the water content increased and then gradually aggregated to form the colloids in the dispersions. To test the photoinduced deformation property, the IAC-4 microspheres were obtained by separating the colloidal spheres from the dispersion and dried appropriately. Upon the irradiation with the linearly polarized laser beam(488 nm, 100 mW/cm²), the microspheres of IAC-4 showed rapid photoinduced deformation parallel to the polarized direction. After the irradiation for 1 min, IAC-4 microspheres were rapidly stretched into the ellipsoidal particles with the average axial ratio of 1.44. With the growth of the irradiation time, the average axial ratio further increased. Finally, the IAC-4 microspheres could evolve into the rod-like particles with the average axial ratio of 3.32 for the irradiation time of 7 min.



Preparation of Carbon Dots from Soy Milk Powder and Fluorescent Nanofibers Containing Carbon Dots^†

GAO Ningxiao,XU Yulong,LIU Yong

2019, 40(3):  555-559.  doi:10.7503/cjcu20180638

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Carbon dots were prepared by using hydrothermal synthesis method with soy milk powder as the carbon source and organosilane as a passivating agent. Electrospinning technology was adopted using carbon dot and polyvinyl pyrrolidone(PVP) blending solution as the spinning solution to prepare nanofibers containing carbon dots. The properties of the carbon dots were characterized by ultraviolet absorption spectroscopy, fluorescence absorption spectroscopy, and fluorescence emission spectroscopy. The results showed that the carbon dot dispersion solution extracted from soy milk powder emitted strong cyan fluorescence under the excitation of 340—540 nm ultraviolet light. The fluorescence emission peak appeared at 550 nm and there was a weak redshift with the increase of excitation wavelength. The obtained carbon-containing nanofibers have a uniform diameter distribution, good morphology, and retain excellent fluorescence properties.



Preparation of Bonded Super-hydrophobic Thin Film^†

MA Haoxiang,LAI Hua,ZHANG Enshuang,LÜ Tong,CHENG Zhongjun,LIU Yuyan

2019, 40(3):  560-566.  doi:10.7503/cjcu20180600

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By combining polydimethylsiloxane(PDMS) and carbon fabric, a superhydrophobic film with repeated adhesion performance was fabricated by the introduction of microarray structure on the PDMS polymer surface with a template method. The results show that the contact angle and rolling angle on the microstructural surface of the thin film are 154° and 14°, respectively, having low adhesion superhydrophobicity performance. The close combination of PDMS and carbon fiber fabric can endow the superhydrophobic film with higher adhesion performance and mechanical property. The breaking strength reaches 116.96 MPa. The as-prepared superhydrophobic film can be adhered on different materials. After long time adhesion of 30 d and repeated adhesion of 50 times, the as-prepared film still maintains high adhesion and superhydrophobic properties, which shows that the superhydrophobic film has good mechanical stability and durability and can meet the requirements of reusability for a long time. It can be used to repair the large-area damaged super-hydrophobic coating quickly and efficiently.



Preparation of Graphene/Carbon Aerogel and Its Applied Research in Multi-frequency Band Electromagnetic Interference

ZHANG Enshuang,LÜ Tong,LIU Tao,HUANG Hongyan,LIU Yuanyuan,GUO Hui,LI Wenjing,ZHAO Yingmin,YANG Jieying

2019, 40(3):  567-575.  doi:10.7503/cjcu20180561

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The graphene/carbon aerogels material was prepared by sol-gel method. The composite aerogels with different hierarchical micro-nanostructures and high conductivity were prepared. Releasing composite aerogels powder in air, the optic attenuation performance of aerogels was measured at infrared, visible and millimeter waves. The results indicated that the shielding ratio of 7%G-CA powder was above 97% and 94%, correspondingly, at the beginning of release and after 20 min, both in infrared and visible wave band. For millimeter wave band, the shielding ratio of 7%G-CA powder is above 75% and 65%, at the beginning of release and after 10 min, respectively. The study is expected to extend application of smoke jamming.



Preparation of Multicolor Electrochromic Polymer Composite Film with Laminated Structure^†

OUYANG Mi,ZHU Rui,LÜ Xiaojing,QU Xingxing,LI Weijun,LI Lin,LÜ Yaokang,ZHANG Cheng

2019, 40(3):  576-582.  doi:10.7503/cjcu20180535

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Two electrochromic polymers,poly(3,4-ethylenedioxythiophene)(PEDOT) and poly{4,4',4″-tris[4-(2-bithienyl)pheny]amine}(PTBTPA)with different neutral absorption spectra and the complementary colors were synthesized via electrochemical polymerization method, respectively. Then the composite film with the laminated structure was controllably prepared by adjusting the electrochemical polymerization parameters. FTIR spectra and SEM images indicate that the laminated composite film is obtained. UV-Vis spectra and electrochemical measurements demonstrate that the composite film exhibits a noticeable electrochromism with reversible color changes from orange, blue to dark green, and maintains good electrochemical activity and optical contrast compared to those of the pristine PTBTPA film and PEDOT film. This work is to provide a simple and efficient method to build the laminated composite structure for achieving multicolor or even full-color electrochromic materials, which is also suitable for other electrochromic polymer systems.



Preparation of Complex Nanogel with Up-conversion Fluorescence-responsive Performance and Its Fluorescence Energy Transfer Behavior^†

LIANG Donglei, SONG Qiusheng, YAO Yutian, LIU Ben

2019, 40(3):  583-591.  doi:10.7503/cjcu20180470

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A functionalized NaYF₄∶Yb³⁺,Er³⁺ nanocrystal was prepared by hydrothermal method and decorated with 3-benzylsulfanylthio-carbonylsufanylpropionic acid(BSPA). Moreover, vinyl functional Rhodamine 6G monomer(R6GHA) was synthesized from rhodamine 6G(R6G) by a series of chemical reactions. Then, a novel complex fluorescent nanogel of NaYF₄∶Yb³⁺,Er³⁺/PNIPAm-co-R6GHA, which possesses multiple response, was prepared by reversible addition-fragmentation chain transfer(RAFT) polymerization and click reaction. In the as-prepared complex fluorescent nanogels, the functionalized nanocrystal and R6GHA form donor/receptor pairs of fluorescence resonance energy transfer(FRET). The microstructure of the nanogels was characterized by transmission electron microscopy(TEM), X-ray diffraction(XRD), Fourier transform infrared spectroscopy(FTIR) and differential scanning calorimeter(DSC). The fluorescence response of the nanogel to pH value, ambient temperature and different metal ions were investigated by photoluminescence(PL) and the mechanism was discussed in detail. The results show that fluorescence emission of the nanogels is influenced greatly by environmental temperature, and the composite nanogels have selective fluorescence response to Hg²⁺. In the presence of H⁺ or Hg²⁺, energy can transfer from the nanocrystals to R6GHA moieties under 980 nm excitation. The detection of the concentration of Hg²⁺ can be achieved by the change of intensity ratio of characteristic fluorescence emission peaks of nanocrystals and R6GHA moieties.



Layer-by-layer Assembled Polymeric Complexes Films for High Loading and Differential Release of Macromolecular and Small Molecular Drugs^†

CHEN Dongdong, SONG Wenzhi, LI Hui, HE Dan, SUN Junqi, YIN Wanzhong

2019, 40(3):  592-600.  doi:10.7503/cjcu20180408

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The layer-by-Layer(LbL) assembled polymeric complexes films capable of differential release of macromolecular and small molecular drugs were fabricated by utilizing chitosan(CHI) hydrochloride-chondroitin sulfate sodium(CSS) complexes(denoted as CHI-CSS complexes) as building blocks and post-diffusion of ceftriaxone sodium(CTX). The CHI-CSS complexes were prepared by pre-assembled macromolecular drugs CSS with CHI, and then were LbL assembled with hyaluronic acid(HA) to produce CHI-CSS/HA polymeric films. The small molecular drugs CTX were loaded into the CHI-CSS/HA polymeric films through a postdiffusion process. The as-prepared CHI-CSS/HA polymeric films possess high loading capacity because of the high encapsulation amount of CSS in CHI-CSS complexes and plenty of electrostatic binding sites for CTX provided by film component CHI. CTX can be quickly released from the polymeric films because of the brea-kage of its electrostatic interaction with film component CHI. Meanwhile, the CSS can be released in sustained manner by enzymatic degradation of the films. The synergetic therapeutic effects can be achieved by fast release of antibiotic drug CTX to effectively eliminate bacteria and by sustained release of CSS to promote wound healing. The present work provides a facile way to fabricate polymeric films for high loading and diffe-rential release of multiple therapeutic agents.



Preparation of Amine-modified Poly(γ-benzyl-L-glutamate) Guided Bone Regeneration Film^†

LU Jiawei,ZHANG Kunxi,YU Xi,YAN Shifeng,YIN Jingbo

2019, 40(3):  601-611.  doi:10.7503/cjcu20180354

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Guided bone regeneration film plays an important role in bone defect reconstruction. In this paper, poly(γ-benzyl-L-glutamate)(PBLG) was used as raw materials to construct dense films and porous films by solvent casting and particle leaching. And the bilayers guided bone regeneration membrane was constructed by ethanolamine amine membrane modification on the surface. The effect of different modification time on the hydrophilicity and mechanical properties of the films was investigated. The results show that with the increase of the molecular weight of PBLG, the mechanical strength of the film increases and the degradation rate is getting slower. Prolonging the time of amine modification can improve the hydrophilicity of the film and the degradation rate both in vivo and in vitro. Through cell experiments, it was found that the dense layer could effectively block the invasion of fibroblasts, and the porous layer can support adherence and spread of cells. Surface-modified PBLG-based materials were demonstrated to be useful for repair of bone defects in vivo by in vitro bioactivity evaluation. The guided bone regeneration membrane constructed has good mechanical properties, degradation performance, and a certain degree of fit with the tissue. And it could effectively inhibit the infiltration of fibroblasts. The membrane has potential application value.



Preparation and Characterization of Pyrrole-(3,4-ethylenedioxythiophene) Copolymer Ordered Nanoarray Film^†

QIAN Ming,XU Zhimin,LIU Weiwei,HAN Bing

2019, 40(3):  612-616.  doi:10.7503/cjcu20180312

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We adopted the anodic aluminum oxide(AAO) template electrochemical deposition method for synthesis of a new type of copolymer nano array membrane structure as lithium ion battery electrode material. This pyrrole-(3,4-ethylenedioxythiophene)(PE) copolymer nano-array membrane material has a lot of advantages, such as better electrochemical properties. The specific capacity can reach 1426.1 mA·h/g(the charge and discharge current density is 100 mA/g) and good cyclic stability(after 300 cycles of charging and discharging, the specific capacity remains above 1400 mA·h/g). Therefore, this multi-component polymer nanowire array may be widely developed for the next generation of long life, high-performance lithium-ion battery electrode materials.