Chem. J. Chinese Universities

Cover and Content of Chemical Journal of Chinese Universities Vol.39 No.6(2018)

2018, 39(6): 0-0.

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Optical Properties and Applications of Halide-perovskite Nanocrystals^†

JI Tianhao, TIAN Yanqing

2018, 39(6): 1113-1120. doi:10.7503/cjcu20170788

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Halide perovskite-type ABX₃ nanocrystals mainly including the optical properties and applications of all-inorganic ABX₃ nanocrystals were reviewed. First of all, the two preparation methods of atmospheric pressure, solvent heating and ion-exchange process for all-inorganic nanocrystals are reported; then, the optical properties of their absorption and photoluminescence are elaborated in detail; finally, their applications in light emitting diode(LED) and solar cell are emphasically elucidated, and also involving in the fields of laser, photodetector and photocatalysis. In the recent future, the halide perovskite nanocrystals will also definitely exhibit other potential applications owing to the excellent optical and electrical properties.

In situ Biomimetic Remineralization of Enamel-like Hierarchical Structures^†

CUI Yan, ZHANG Kai, CHEN Yixin, SUN Hongchen, HUANG Yang, WANG Dandan

2018, 39(6): 1121-1126. doi:10.7503/cjcu20180171

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The in situ regeneration of enamel-like hierarchical structures were carried out under biomimetic condition using etched enamel as the template. The morphology, chemical composition, mcriohardness, biocompatibility and mechanical properties of the remineralized layer were investigated by scanning electron microscopy(SEM), energy dispersive spectroscopy(EDS), X-ray diffraction(XRD) and Fourier transform infrared spectroscopy(FTIR). Furthermore, the enamel layers remineralized under biomimetic conditions and hydrothermal condition were compared. The results showed that the structure of them were similar to that of the natural enamel prisms and interprisms, and the crystal composition were both mainly fluorapatite. However, the structures, morphology and microhardness of enamel-like hierarchical enamel layer were better than those of the enamel layer obtained under hydrothermal condition.

Synthesis of Zeolite β@IISERP-COF2 Core-shell Hybrid Materials^†

HUANG Weiwei, REN Jiawang, FANG Qianrong, Valentin VALTCHEV

2018, 39(6): 1127-1131. doi:10.7503/cjcu20180071

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Zeolite β was crystallized from precursor solutions within the pores of anion exchange resin beads. Resin beads as sacrificial template was removed by calcination leaving stable beads of zeolite β. We use the zeolite β beads as substrate to cover a layer hydrophobic IISERP-COF2, termed as zeolite β@IISERP-COF2. There is definite advantage in transferring the hydrophobicity of COFs to zeolite to aid their adsorb CO₂ in humid environment. Water adsorption capacity(measured under 79% humidity) of zeolite β@IISERP-COF2(2.1%) shows a significant decrease compared to that of zeolite β(11.0%).

Highly Efficient Utilization of Rice Husk Char to Prepare Carbon Adsorbent and Calcium Silicate^†

CHENG Yanyan, SUI Guanghui, CHEN Zhimin, LIU Huan, DUAN Yajun, WANG Xiaofeng, YANG Xiaomin, WANG Zichen

2018, 39(6): 1132-1137. doi:10.7503/cjcu20170796

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A highly efficient method for the comprehensive utilization of rice husk pyrolysis char was reported. Rice husk pyrolysis char was used as C and Si resource. C and Si in rice husk pyrolysis char were separated via the reaction of rice husk pyrolysis char and sodium hydroxide to form carbonaceous matter and sodium silicate. Carbonaceous matter was activated into adsorbent carbon by surface modification of alkali solution. Sodium silicate was converted into calcium silicate by the reaction with calcium oxide. The sodium hydroxide solution was recycled. The adsorption performance of the adsorbent carbon was investigated by the decolourization ratio of malachite green solution. The results show that the decolourization ratio of malachite green solution can achieve 99.9% under the optimized conditions(pH=7, 30 ℃, 60 min). The structures of calcium silicate prepared at different temperatures and Ca/Si ratios were studied by X-ray diffraction. The results show that the structure of calcium silicate is associated with the Ca/Si ratio and heating treatment temperature. α_L'-Ca₂SiO₄ was obtained when the Ca/Si molar ratio was 3 and the heating treatment temperature was 800 ℃. Effect of Ca/Si molar ratio, reaction temperature and time on the recovery rate of alkaline was investigated by statistical method. The influence order is Ca/Si molar ratio> temperature > time. The recovery rate of alkaline can reach 100% under the optimized conditions(Ca/Si molar ratio of 3, 90 ℃, 1 h).

Proton Conduction Property of a Manganese Phosphite Open Framework Compound^†

WANG Zhixiu, MU Ying, WANG Yilin, SUN Xiaoyuan, SU Tan, LIU Jingyao

2018, 39(6): 1138-1144. doi:10.7503/cjcu20170645

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An open-framework manganese(Ⅱ) phosphite, ??NH₄??₄[Mn₄(PO₃H)₆](JIS-10), was synthesised via ionothermal method using 1-pentyl-3-methylimidazolium bromide([Pemim]Br) as the solvent and the proton conduction property of the crystal was studied. The proton conductivity of the as-synthesized JIS-10 is increased from 5.32×10^-4 S/cm(7 d) to 1.065×10^-3 S/cm(60 d) at 98% relative humidity, the saturation degree of absorbed water plays an important role in the enhancement of conductivity. While in an anhydrous atmosphere, JIS-10 hardly conducts electricity.

Electrochemical Extraction of La and Zn-La Alloy Codeposition in Chloride System^†

XUE Yun, CAO Meng, YANG Xue, XU Yanlu, YAN Yongde, JI Debin, MA Fuqiu

2018, 39(6): 1145-1151. doi:10.7503/cjcu20170605

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The electrochemical behavior of La(Ⅲ) ions was studied in LiCl-KCl and LiCl-KCl-ZnCl₂ melts on the Mo electrode at 723 K by cyclic voltammetry, square-wave voltammetry and open-circuit chronopotentiometry. The results showed that the reduction of La(Ⅲ) to La(0) is a one-step irreversible reaction controlled by diffusion. In LiCl-KCl-ZnCl₂ solutions, the underpotential deposition of La formed four kinds of Zn-La intermetallic compounds on pre-deposited Zn. Zn-La alloy was obtained by galvanostatic electrolysis at 923 K. The microstructure and micro-zone chemical analysis of Zn-La alloy were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM) and energy dispersive spectrometry(EDS). Based on the previous electrochemical results, square-wave voltammetry was used to determine the concentration changes of La during potentiostatic electrolysis, the concentration of La(Ⅲ) was close to zero, and the extraction efficiency was 99.55% after potentiostatic electrolysis for 50 h.

Contact Potential Barriers and Photoelectric Properties of Pt-TiO₂ Nanotubes^†

WENG Qing, LI Jingling, LIAO Wei, YU Hualiang, YU Qiaoying

2018, 39(6): 1152-1157. doi:10.7503/cjcu20170517

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Composite TiO₂ nanotubes of Pt-modified(Pt-TNT) were synthesized via alkaline fusion-hydrothermal method under ambient atmosphere pressure. The microstructure morphology and properties of Pt-TNT were characterized. Composition analysis showed that the particulate matters on surface of Pt-TNT were composed of platinum and platinum oxides(Pt, PtO and PtO₂, Pt $O x δ +$ ). Contact potential barriers consisting of Pt $O x δ +$ -anatase-rutile-Pt $O x δ +$ are presumed to form upon Pt $O x δ +$ particle that deposited on the surface of Pt-TNT. The result of XRD indicated that a mixture of anatase and rutile phases prevailed in Pt-TNT. The 1047 and 1641 cm^-1(OH bending vibration) of FTIR were caused by the adsorption of δ-H₂O on the surface of Pt-TNT. Surface photovoltage spectroscopy(SPS) and electric field-induced surface photovoltage spectroscopy(FISPS) demonstrated that the bound exciton which showed sub-band gap transition characteristics with the asymmetric changes of photoelectric property corresponding to changes in polarity and strength of the external electric field. Compared with TiO₂, BET of Pt-TNT increased more than 3.55 times and was 41 m²/g by nitrogen adsorption.

Live-cell Synthesis of ZnSe Quantum Dots in Staphylococcus aureus^†

ZHANG Yanan, YANG Lingling, TU Jiawei, CUI Ran, PANG Daiwen

2018, 39(6): 1158-1163. doi:10.7503/cjcu20180127

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Staphylococcus aureus cells were skillfully utilized to produce ZnSe quantum dots and transformed into fluorescing cells through temporally-spatially coupling strategy. The products were characterized by means of transmission electron microscopy(TEM), atomic force microscope(AFM), dynamic light scattering(DLS), inductively coupled plasma emission spectrometry(ICP-AES), UV-Vis absorption spectroscopy and photoluminescence(PL) spectroscopy. ZnSe QDs biosythesized by such a method possess uniform particle size of (2.96±0.76) nm and good dispersibility with fluorescence emission at 537 nm.

Enantioseparation of Seventeen Kinds of β-Lactams on Carboxymethyl-β-cyclodextrin Chiral Stationary Phase and Research on Enantioseparation Mechanism

ZHOU Min, XU Xiaoying, LONG Yuande

2018, 39(6): 1164-1171. doi:10.7503/cjcu20170810

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A reversed phase high performance liquid chromatographic method was developed using carboxymethyl-β-cyclodextrin chiral stationary phase for enantioseparation of seventeen kinds of cis-β-lactams enantiomers. Most of the compounds could get base-line separation. The effects of mobile phase pH, salt type and concentration, as well as mobile phase proportion were discussed. The results showed that(0.10% NH₄Ac+FA)(pH=5.0)-MeOH(70∶30, volume ratio)was the optimum condition for most of chiral compound. Under the optimum condition, the 7 compounds for CA series could get base-line separation except for compound 18CA, the best resolution values for compounds 15CA and 17CA were 1.71 and 1.74, respectively. The resolution values for seven EA compounds were between 1.00 and 1.50 which was nearly close to base-line separation except for compounds 18EA and 22EA. The resolution values for three BA compounds were close to 1.00. Structures of analytes also played important role in chiral separation. The results indicated that better resolution could be obtained if the analyte with proper size matching cyclodextrin cavity. Hydrogen bond interaction between the substituents on the cyclodextrin derivative and the analytes and smaller steric hindrance were also good for enantioseparation. Smaller steric hindrance making analytes easily penetrate into cyclodextrin cavity was beneficial to enantioseparation. A tentative chiral recognition mechanism was proposed after a comprehensive analysis of the influencing factors for enantioseparation using compound 15CA as example. Inclusion interaction, hydrogen bond interaction, dipole-dipole interaction and steric hindrance were found to exert synergistic effects on enantioseparation. However, the inclusion interaction between the analytes and the cyclodextrin was the primary role for enantioselective recognition. In comparison with native β-CD CSP, CM-β-CD CSP exhibited enhanced enantioseparation.

Rapid Detection of Three Chemical Components Added Illegally into Antihypertensive Health Food by TLC Concentration in situ Combined with Micro-Raman Spectroscopy Method^†

XU Feng, LI Xiaoxue, LI Li, LIU Jicheng

2018, 39(6): 1172-1177. doi:10.7503/cjcu20170735

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A thin layer chromatography(TLC) combined with micro-Raman spectroscopy technology was applied for the detection of three chemical components(nimodipine, lacidipine and nitrendipine) added illegally into the antihypertensive health food by concentration in situ and six kinds of antihypertensive health food products were tested. The doping ingredient and substrate were separated initially by TLC with silica gel 60F₂₅₄ aluminum alloy plates as the stationary phase, [V(cyclohexane)∶V(acetic ether)=5∶4] as the developing solvent, and using UV light(254 nm) to view and locate. Then the spots of the trace of doping ingredient were concentrated on the TLC plate with acetone, and the concentrated points were detected directly by the micro-Raman spectroscopy with laser source of 780 nm, objective of 10×, spectral range of 100—3300 cm^-1, laser power of 24.0 mW, exposure time of 0.05000 s and number of scans of 30. The results show the common substrate in the antihypertensive health food products had no interference with the detecting results of doping components. The LOD was 2—4 μg. The method is accurate, sensitive, simple and rapid, and can provide a new reference method for the technology research of rapid detection of the ingredients added illegally in the antihypertensive health food.

Fluorescence Spectroscopic Analysis on the Synergistic Mechanism of Diazepam and Ethanol^†

CUI Shengfeng, WAN Jingwei, ZHOU Chenghe

2018, 39(6): 1178-1184. doi:10.7503/cjcu20170710

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The synergistic mechanism of diazepam and ethanol was investigated based on fluorescence spectroscopic method by simulating the physiological environment in vitro and the in vivo experiments in mice. The experimental results revealed that the presence of ethanol in the blood can reduce the equilibrium binding constant of diazepam-HSA complex in the early metabolism of diazepam, which resulted in the increase of the free diazepam proportion, accelerating the metabolic rate of diazepam, and shorten the half-life and storage time of diazepam in the blood, thereby enhancing its bioactive efficacy.

Discovery and Activity Verification of a O-GlcNAc Transferase Inhibitor by Structure-based Virtual Screening^†

LIU Yubo, ZHANG Nana, CHEN Jinjiao, ZHU Tong, ZHANG Jianing, LI Wenli

2018, 39(6): 1185-1190. doi:10.7503/cjcu20170819

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A specific natural-product O-GleNAc transferase(OGT) inhibitor(Amentoflavone, AF) was identified from a structure-based virtual screening analysis. X-ray structure of the human OGT binding to uridine diphosphate(UDP) was used as the receptor in Discovery Studio 4.5. AF effectively inhibited OGT in a dose dependent and time dependent manner in vitro. The IC₅₀ value of this compound was 48.1 μmol/L. Western blot showed that O-GlcNAc modification of Nup62 by OGT in a cell free reaction system was decreased along with a shift in molecular weight by AF treatment. Furthermore, AF reduced global O-GlcNAcylation in a dose and time-dependent manner in Cos7 cells. Molecular dynamics analysis suggested that AF might form multiple hydrogens bonds with OGT in the same positions as the sugar donor UDP. This study validated the use of structure-based molecular docking to discover novel inhibitors of OGT. AF may be employed as a useful scaffold for the development of more potent OGT inhibitors in the future.

Synthesis of 4,13-Dithio Benzene and-18-Crown-6 and Its Selective Extractability on A

g + †

TIAN Huan, ZHANG Menglong, WANG Lisha, TONG Bihai, ZHAO Zhuo

2018, 39(6): 1191-1196. doi:10.7503/cjcu20170760

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4,13-Dithio benzene and-18-crown-6(DSB18C6) was synthesized by esterification, reduction and nucleophilic substitution reaction. The structural characterization was performed using proton nuclear magnetic resonance spectroscopy and X-ray single crystal diffraction, the selective binding to Ag⁺ was investigated by solvent extraction. The results show that DSB18C6 has a high selective extraction ability for Ag⁺ in the co-existence of Cu²⁺, Pb²⁺, Zn²⁺ and Ni²⁺ ions. The extraction efficiency of DSB18C6 to Ag⁺ was 95%.

Syntheses and Bioactivities of Myricetin Derivatives Containing Piperazine Acidamide Moiety^†

RUAN Xianghui, ZHAO Hongju, ZHANG Cheng, CHEN Lijuan, LI Pu, WANG Yihui, HE Ming, XUE Wei

2018, 39(6): 1197-1204. doi:10.7503/cjcu20170740

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Thirteen novel derivates of piperazine acidamide myricetin were synthesized with the raw materials of myricetin, piperazine and aromatic acids. First, the myricetin of high selectivity was obtained through methylation protection hydroxyl and deglucoside. Then, the intermediate underwent three-steps substitution reaction with the piperazine and various aromatic acids to form target compounds. Inhibitory activities of compounds on proliferation of human breast cancer cell line(MDA-MB-231) were tested by methyl thiazolyl tetrazolium(MTT) colorimetric assay in vitro. The experimental results demonstrated that most of the myricetin derivatives exhibited good inhibitory activity. Inhibitory activities of compounds 4a and 4i with the concentration of 1 μmol/L were higher than epirubicin hydrochloride as positive control drug, and the corresponding inhibitory activities were up to 86.7% and 83.6% at 10 μmol/L, respectively.

Effect of Different Force Fields on B-DNA to A-DNA Conversion^†

ZHANG Hong, CAI Wensheng, SHAO Xueguang

2018, 39(6): 1205-1211. doi:10.7503/cjcu20180201

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The aim of the present work is to investigate and compare the effect of the latest CHARMM and AMBER force fields(including bsc1 and OL15) on the B-DNA to A-DNA conversion through exploring the free-energy changes of the conversion process. The extended adaptive biasing force(eABF) method was utilized to perform the free-energy calculations. The results showed that the free-energy profiles characterizing the transition differ significantly for these two force fields. The AMBER force field performs better than the CHARMM force field in aqueous solution. The structure near the global minimum of the free-energy profile by the AMBER force field presents B-form, in agreement with the experimental results, while the most stable structure by the CHARMM force field locates between A- and B-form. Deep analysis of the radial distribution functions of the counterions around DNA reveals that the distribution of counterions in minor groove using the CHARMM force field is lower than that using the AMBER force field. Therefore, for the CHARMM force field, the repulsion of phosphates backbone could not be properly counteracted by counterions, as a result, the minor groove becomes wider, causing a slight conformational change towards A-form.

Kinetic Mechanism Study on Low Temperature for Decalin Combustion^†

LI Yingli, WANG Jingbo, LI Xiangyuan

2018, 39(6): 1212-1220. doi:10.7503/cjcu20180160

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The kinetic mechanism of low-temperature decalin combustion was studied, including reaction types such as dehydrogenation reaction, radical oxygenation reaction and 1,5 H-shift reaction. The thermodynamic parameters of species were obtained at CBS-QB3 level. The high pressure limit rate constants for reactions with transition state were obtained by transition state theory calculations, while the rate constants for barrierless reactions were obtained by variational transition state theory. Based on this mechanism, the kinetic and thermodynamic behavior of decalin oxidation reactions at low temperature were analyzed. Compared with the corresponding results from linear alkanes and monocycloalkane, the rate constants of O₂-addition to decalin radical change more fast with temperature and the energy barriers of 1,5 H-shift reactions are higher, which reveal the influence of reactant structure on kinetics. The analysis result of thermodynamic equilibrium constants showed that the O₂-addition reaction to decalin radical plays a leading role at low temperature. The rate constants of Arrhenius form for all reactions were fitted and these parameters can be used in the construction and optimization of low temperature combustion mechanism of bicycloalkane.

Effect of Heterogeneous Inducing Bilayer on the Properties of Rubrene Thin Film Transistors^†

SUN Yang, YAN Chuang, XIE Qiang, SHI Chao, ZHANG Liang, WANG Lijuan, SUN Lijing

2018, 39(6): 1221-1227. doi:10.7503/cjcu20180092

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Inducing growth method was used to improve the crystallinity of rubrene thin films. Heterogeneous inducing bilayers were formed with vacuum deposition p-sexiphenyl(p-6P) and copper phthalocyanine(CuPc) on silicon dioxide substrates. The influence of various substrate temperatures on the morphology of rubrene films was investigated. And the growth process of rubrene molecules on heterogeneous inducing bilayer was analyzed. The results showed that the crystalline rubrene films were formed by the partly ordered films of the second CuPc inducing layer. The ordered areas of CuPc films increased with the substrate temperature. The rod-like crystals of rubrene films also gradually became larger. When the substrate temperatures of CuPc and rubrene were both 90 ℃ and the rubrene thickness was 20 nm, the rubrene films formed highly ordered and interconnected rob-like grains with desirable molecular orientation. The rubrene films on heterogeneous bilayers were polycrystalline structure by X-ray diffraction and transmission electron microscope analyses. And the performance of organic thin film transistor devices with the heterogeneous bilayer was obviously improved. The open-state current was improved by about 3 orders of magnitude, the mobility was raised by 30 times, and the threshold voltage was reduced by 20 V.

Measuring the Reaction Rates of High Affinity Reactions by Single-molecule Magnetic Tweezers^†

LU Yue, MA Jianbing, HUANG Xingyuan, XIAO Xue, LI Ming, LU Ying, XU Chunhua

2018, 39(6): 1228-1234. doi:10.7503/cjcu20180083

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A method based on single molecule experiment was adopted. Single-molecule magnetic tweezers was used to study the different binding process of SSB(E. coli single-stranded DNA binding protein) and ssDNA(single-stranded DNA) in different conditions, and get the reaction rate and reaction detailed information. This method can be used in similar reactions.

Synthesis of a Core-shell Structured Ag/ZIF-8 Catalyst with Mesoporous Silica Shell^†

XIAO Shanshan, OUYANG Yiting, LI Xiaoyun, WANG Zhao, WU Pan, DENG Zhao, CHEN Lihua, SU Baolian

2018, 39(6): 1235-1241. doi:10.7503/cjcu20170811

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The self-assembly technique was employed to sythesize the Ag nanoparticles on ZIF-8(Ag/ZIF-8). Cetyltrimethyl ammonium bromide(CTAB) was used as the structure-directing agent to facilitate mesoporous silica to coat on the surface of hydrophobic Ag/ZIF-8(Ag/ZIF-8@MS). The prepared Ag/ZIF-8@MS with a core-shell structure was characterized by a series of measurements. The results show that Ag/ZIF-8@MS has a uniform particle size(Ag/ZIF-8@MS: ca. 100 nm, Ag: ca. 15 nm), high specific surface area(539 m²/g) and large pore volume(0.64 m³/g). The TEM images indicate that the thickness of mesoporous silica shell is ca. 20 nm. The structure of catalyst is transformed into Ag/ZnO@MS core-shell structure after calcination at 550 ℃. Meanwhile, both of the Ag-baesd catalysts were tested for the reaction of 4-nitrophenol to prepare 4-aminophenol. The catalytic results showed that the conversion of 4-nitrophenol catalyzed by Ag/ZIF-8@MS was more than 95%, which proves the advantage of the core-shell structure with ZIF-8 as a carrier.

Preparation and Electrochemical Properties of Rice Husk Based Activated Carbon Modified by Pitch^†

LIU Yanhua, JIN Lu, XUE Beichen, GUO Yupeng

2018, 39(6): 1242-1248. doi:10.7503/cjcu20170763

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Coal tar pitch with high carbon content and good conductivity were used as surface coating agents to modify rice husk-based activated carbon(RHAC) by low temperature mixing and medium temperature curing. The experimental results show that the optimum mixing mass ratio of pitch to RHAC is 1∶5, in the organic electrolyte 1 mol/L of Et₄NBF₄/PC system, the volumetric capacitance from the original 67.54 F/mL to 84.34 F/mL. The volumetric capacitance was significantly increased. In addition, in the cyclic stability test, the capacitance retention rate of pitch-coated activated carbon was 91.52%, which was higher than that of unmodified activated carbon(84.11%) after 10000 cycles at the current density of 1 A/g. This method has greatly improved the electrochemical performance of rice husk-based activated carbon, which is simple and easy, green and pollution-free, provides a feasible method for the industrial production.

Enhanced Hydrogen Evolution Catalytic Activity of Cobalt-embedded Carbon Nanotubes by Thermal Vacuum Activation^†

ZOU Jiayun, LIU Yipu, CHEN Hui, LI Guodong

2018, 39(6): 1249-1254. doi:10.7503/cjcu20170715

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Cobalt-embedded carbon nanotubes with high catalytic activity were prepared by a facile thermal vacuum activation method. After the vacuum activation, intrinsic carbonaceous defects of the cobalt-embedded carbon nanotubes increased, resulting in greatly improved catalytic activity(>7-fold). The characterizations of high resolution transmission electron microscopy(HRTEM), X-ray photoelectron spectroscopy(XPS) and Raman spectroscopy revealed that the thermal vacuum post-treatment can lead to a great amount of intrinsic carbonaceous defects, which further relates to more catalytically active sites and thus enhances the interfacial electron-transfer properties, resulting in improved catalytic activity.

Antioxidant Property of Catalyzed Lignosulfonate Using S₂

O 8 2 -

/ZrO₂ Doped Cerium as Catalysts^†

ZHANG Yan, ZHANG Shengming, FANG Guizhen

2018, 39(6): 1255-1259. doi:10.7503/cjcu20170746

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To improve catalysis activity of S₂ $O 8 2 -$ /ZrO₂ for the hydrogenation of lignosulfonate, rare earth cerium was doped onto the catalysts. Through Hammett indicator method and the determination of X-ray small diffraction(XRD), specific surface area(S_BET) and sulfur content, the influence of different Cerium doping ratio on the acid strength of solid acid, carrier crystal type and S_BET were discussed. Doping cerium promoted to form amorphous ZrO₂ crystal, contributed to increasing S_BET and sulfur content for solid acid enhancement. The contents of phenol hydroxyl and total hydroxyl were considered as a fractions of active groups in lignin, increased from 1.52% and 2.31% to 3.35% and 10.35%, combined with the data of ¹H nuclear magnetic spectra(¹H NMR). The results proved that the cerium doping improved S₂ $O 8 2 -$ /ZrO₂ catalytic properties through increasing the hydroxyl groups content of lignosulfonate. It confirmed that the catalyst coping Cerium was an excellent catalyst for hydrogenation of lignosulfonate dispersing in water. And hydroxylated ligno-sulfonate has good antioxidant capacity.

Inhibition Effect of Polyvinylpyrrolidone on Corrosion of Reinforcing Steel in Simulated Concrete Pore Solutions^†

DONG Shigang, GAO Yingbo, GUAN Zichao, WANG Haipeng, WANG Xia, DU Ronggui, SONG Guangling

2018, 39(6): 1260-1266. doi:10.7503/cjcu20170648

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Surfactant polyvinylpyrrolidone(PVP) was used as a potential corrosion inhibitor for reinforcing steel. The corrosion inhibition effect and mechanism of PVP for the reinforcing steel in the simulated polluted concrete pore solution at pH=11.0 with 0.5 mol/L NaCl were studied by electrochemical impedance spectroscopy and polarization curve measurements, scanning electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy. The results indicated that the PVP concentration had an important effect on the corrosion behavior of the steel in the solution. The PVP with the optimum concentration could effectively inhibit the corrosion of the reinforcing steel. The inhibition efficiency of PVP reached 89.1% when its concentration was 25 mg/L. PVP formed an adsorption film on the surface of the reinforcing steel and protected the steel from corrosion.

Preparation and Electrochemical Energy Storage Performances of LiNi_0.8Co_(0.2-2_x₎Al_xMn_xO₂ Cathode Material^†

LI Huan, JIANG Qi, QIU Jiaxin, LIU Qingqing, GAO Yike, LU Xiaoying, HU Ailin

2018, 39(6): 1267-1273. doi:10.7503/cjcu20170533

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A series of LiNi_0.8Co_(0.2-2_x₎Al_xMn_xO₂(x=0, 0.005, 0.01, 0.025, 0.04, 0.05) materials was prepared by high temperature solid phase method. The morphology, structures and electrochemical performances of the materials were characterized. The results showed that all the obtained materials had α-NaFeO₂ structure and the degree of lithium nickel cation mixing decreased first and then increased with the increase of manganese, aluminum elements along with cobalt element decreasing. When x was equal to 0.01, the material had the lowest degree of lithium nickel cation mixing, the smallest charge transfer impedance and larger lithium ion diffusion coefficient. And the material exhibited the best electrochemical performances and stability among the obtained materials: its discharge capacity was up to 175.2 mA·h/g at 0.1C; the capacity retention rate was up to 92.7% after 50 cycles at 0.2C.

Polyethyleneimine Functionalized Graphene Oxide Against hIAPP Amyloid Aggregation^†

LU Tong, WANG Chunyang, ZHU Zhihui, JIANG Wei, HUO Mingnan, LI Fei

2018, 39(6): 1274-1280. doi:10.7503/cjcu20180166

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Preventing human islet amyloid polypeptide(hIAPP) fibrillogenesis has been a primary strategy in development of therapeutic drugs for type Ⅱ diabetes. In this study, we prepared stable GO-PEI complex by modification of polyetherimide(PEI) on the surface of graphene oxide(GO) using covalent binding method. The results of transmission electron microscopy(TEM) and circular dichroism(CD) show that GO-PEI is more efficient than GO in inhibiting hIAPP fibril formation. The ThT fluorescence assay and atomic force microscopy(AFM) image data show that GO-PEI is the most effective for the inhibition of hIAPP fibrillation when it is added at the initial stage of hIAPP aggregation, and less effective when added in the growing period of hIAPP aggregation, but the inhibitor disables to disrupt the matured hIAPP fibrils. The findings may provide information valuable to the research and development of GO-based inhibitors.

Precise Controllable Post-sulfonation for Preparation of Sulfonated Poly(arylene ether sulfone)s and Their Properties for Proton Exchange Membrane^†

XIAO Lei, ZHANG Chen, HE Meiyu, CHEN Kangcheng

2018, 39(6): 1281-1289. doi:10.7503/cjcu20170842

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A series of poly(arylene ether sulfone)s with high molecular weight was prepared from 4-fluorophenyl sulfone, 4,4'-biphenol and bis(4-hydroxyphenyl) sulfone with different mole ratio. Due to the large difference between the electronic effects of biphenyl fragment and phenyl sulfone fragment on the polymer, the sulfonation reaction is easily carried out on biphenyl fragments with higher electron cloud density. The sulfonic acid groups were introduced to ortho-position of the oxy ether group on the biphenyl and sulfonation degree were successfully predicted after post-sulfonation process. Sulfonated polylarylene ether sulfone(SPAES)-based proton exchange membranes(PEM) were prepared by solution casting method, of which relative viscosity, ion exchange capacity(IEC), water uptake and swell ratio, proton conductivity, oxidative stability, mechanical properties and cell performance were investigated. Relative viscosity of sulfonated copolymers was higher than 1.2 dL/g. The sulfonated copolymers showed that titration and ¹H nuclear magnetic resonance calculated value of IEC were accordingly to that of theoretical. Water uptake and swell ratio obviously increased with increasing of IEC and temperature, and the size change ratio of the thickness direction was larger than that of plane direction in the membranes. The thermal gravimetric analyse(TGA) results indicated that the PEMs have the decompose temperature at about 280 ℃. All the PEMs showed maximum tensile strength above 50 MPa, and the elongation at break over 15% at 20 ℃ and 20% RH. Free radical oxidative stability test showed the PEMs with low IEC become brittle in Fenton’s reagent over 200 h at 20 ℃. The proton conductivity of PEMs were increased rapidly with the increase of the IEC and temperature, for example, the conductivity of M2-SPAES(1.34 mmol/g) and M4-SPAES(1.60 mmol/g) were 68 and 89 mS/cm at 60 ℃ in water, and 99 and 129 mS/cm at 80 ℃ in water, respectively. H₂/O₂ Fuel cell performance showed that the open circuit voltage and maximum power output were higher than 1.0 V and 0.54 W/cm² under 60 ℃, 80% RH and 0.1 MPa back pressure, respectively.

Nonisothermal Crystallization Kinetics of ABS/PET/PETG Alloy^†

WANG Meilin, LIU Yudong, LIU Xiaoli, LI Zhiying, LIU Fengqi

2018, 39(6): 1290-1296. doi:10.7503/cjcu20170832

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Acrylonitrile-butadiene-styrene(ABS)/polyethylene terephthalate(PET) alloy were compatibilized by polyethylene terephthalate-1,4-cyclohexanedimethanol(PETG). The effects of the amount of PETG on the mechanical properties were investigated. The nonisothermal crystallization kinetics of PET, ABS/PET and ABS/PET/PETG were studied via different scanning calorimeter(DSC). The Jeziorny method was employed to analyze the nonisothermal kinetics of alloys, and the corresponding kinetic parameters were obtained by calculation. The results showed that the impact strength and elongation at break were increased significantly along with the amount of PETG. But the tensile strength and flexural strength were slightly lower. The crystallinity decreased and the crystallization rate decreased slightly with the amount of PETG increased.

Synthesis of Cyclic and Linear Block Copolyesters via Ring-opening Copolymerization of ε-Caprolatone and L-Lactide Catalyzed by Zinc Complex^†

LI Juan, DU Fanfan, FENG Rui, HU Qian, JIE Suyun, LI Bogeng

2018, 39(6): 1297-1304. doi:10.7503/cjcu20170792

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In combination with methyllithium, ring-opening polymerization(ROP) of L-lactide(L-LA) and copolymerization of ε-caprolactone(ε-CL) and L-LA were investigated in the presence or absence of benzyl alcohol by using an air-stable zinc complex bearing(benzimidazolyl)pyridine alcohol ligand. Similar to the polymerization of ε-CL, the monomers were completely converted to polymers in short time in all the cases and high catalytic activities were achieved in the ROP of L-LA. The structural analysis of polymers indicated that in the absence of benzyl alcohol, the polymers obtained were mainly cyclic PLA with relatively broad molecular weight distribution, whereas linear PLA with lower molecular weight and narrower molecular weight distribution predominated in the presence of benzyl alcohol. On the basis of ROP of ε-CL and L-LA, the ring-opening copolymerization of ε-CL and L-LA was studied with the different CL/LA feeding ratios. A series of linear and cyclic block copolymers with different CL/LA molar ratios was synthesized by the sequential feeding strategy according to the presence or absence of benzyl alcohol in the reaction system. The structure and thermal properties of homopolymers and copolymers were characterized by FTIR, ¹H NMR, ¹³C NMR, GPC, DSC and TGA analysis.

Preparation and PTC Properties of HIPS/HDPE/CB Composites^†

QIN Yanli, XU Haiping, QIU Houtian, ZHAI Yue, DAI Xiujuan, YANG Dandan, WANG Jingrong

2018, 39(6): 1305-1310. doi:10.7503/cjcu20170751

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Polymer-based positive temperature coefficient(PTC) composites were prepared by melting blending with high impact polystyrene(HIPS) and high density polyethylene(HDPE) as matrix, carbon black(CB) as conductive filler. The selective distribution of CB in two-phase matrix composite was characterized by scanning electron microscopy(SEM). The PTC performance of composite with different contents of CB was studied by thermistor resistivity-temperature(RT) curve tester. The results show that after adding HDPE in HIPS/CB system, the percolation threshold of HIPS/CB/HDPE composites decreases, the PTC intensity increases and the capability of voltage-withstanding also is improved.

Preparation of Functional Patterned Protein Arrays via the Combination of Inverse Emulsion and Breath Figure Method^†

DING Lingyun, JU Yuanlai, SUN Wei, CHEN Ji

2018, 39(6): 1311-1318. doi:10.7503/cjcu20170742

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We established a modified breath figure(BF) method using inverse emulsion as casting solution to achieve directed assembly of water-soluble components with the BF arrays. It is a one-step technique with great ease of fabricating regular arrays of biomolecules via self-assembly. To be specific, we constructed a hybrid structured film made from polylactic acid(PLA)/chitosan(CS)/bovine serum albumin(BSA) mixing emulsion. CS particles were synthesized to serve as stabilizers for the inverse emulsion of water-in-oil type and BSA was selected as model protein to be carried within the emulsion water droplets. It has been proved that the CS particles could not only effectively contribute to stabilize the inverse emulsion, but also be able to improve the regularity of the obtained BF arrays. Furthermore, the influencing factors of BSA concentration and water-to-oil ratio were carefully tuned to study their effect on the obtained surface morphology. The results showed that the increase of the BSA concentration and the water-to-oil ratio would both compromise the regular arrangement of the surface pore arrays. But if the concentration and ratio were both increased to a high level, the regular BF arrays would reappear. We tagged the BSA with fluorescent probe to track the assembled morphology of the BSA within the porous polymer matrix. And 3D ring-like arrays of the fluorescent protein were observed under confocal microscope, indicating the success of obtaining the protein arrays via a one-step technique.

Synthesis and Properties of Water-soluble Glycosyl Fluorescent Polymer with Aggregation-induced Emission Effect^†

LING Yao, LIU Xuejing, HAO Haijing, HAO Xiaohui, BAI Libin, WU Yonggang

2018, 39(6): 1319-1325. doi:10.7503/cjcu20170747

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A glycopolymer{poly[2-(2,3,4,6-four-O-acetyl-α-D-mannopyranose) ethyl methacrylate]-tetraphenylethene}(PAcManEMA-TPE) with defined structure was synthesized by one-pot method, which the reduction of dithioester and Click reaction between thiol and epoxy group were conducted simultaneously. The water-soluble glycopolymer(poly[2-(2,3,4,6-four-O-acetyl-α-D-mannopyranose) ethyl methacrylate]-tetraphenylethene)(PManEMA-TPE) was obtained in a high yield(90%) after the deprotection reaction of PAcManEMA-TPE was carried out. The structure and aggregation-induced emission(AIE) of PManEMA-TPE were characterized by Fourier transform infrared spectrometer, nuclear magnetic resonance spectrometer, gel permeation chromatograph, UV-Vis spectroscopy and photoluminescence. Moreover, the cell toxicity of PManEMA-TPE was assayed by MTT, proving its non-toxicity and showing its potential application as a biomedical probe.

Preparation and Properties of Antibacterial Coating with Redox-responsive Drug Releasing Function Based on Macromolecule Self-assembly Colloidal Particle^†

LI Yang, ZHU Ye, MENG Long, WEI Wei, LUO Jing, LIU Xiaoya

2018, 39(6): 1326-1333. doi:10.7503/cjcu20170703

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Bacterial infection and the question(such as inflammation, fever and pain) caused by bacterial infection on the surface of implant metal material have become a major concern. In this study, by ultilizing electrodeposition, a colloidal particles based antibacterial coating with redox-responsive drug releasing property was prepared aiming at improving the adhesion of bacteria and subsequent formation of biofilms onto implant surfaces. Firstly, redox-responsive amphiphilic random copolymer poly-1-bromododecylmethylethylenediethacrylate quaternary ammonium salt-co-N-[2-(pyridine-2-disulfonyyl)-ethyl]-acrylamide-co-methyl acrylate(PPDM) was synthesized by a conventional free radical polymerization using bactericidal moiety 1-bromododecylmethyldimethylethyl quaternary ammonium salt(DMAC₁₂), redox-responsive moiety N-[2-(pyridine-2-disulfonyyl)-ethyl]-acrylamide(PDSA), and methyl methacrylate(MMA) as monomers. Proton nuclear magnetic resonance spectrometer(¹H NMR), Fourier transform infrared spectroscopy(FTIR) and gel permeation chromatography(GPC) were used to confirm the synthesis of PPDM. Then, the resultant copolymer and drug paracetamol(PCTM) were self-assembled together into PCTM-loaded colloidal particles(CPs). The size, morphology and drug-loading efficiency of CPs were characterized by zeta potential and nanoparticle size analyzer, transmission electron microscope(TEM) and UV irradiation. Finally, the PCTM-loaded PPDM coating was prepared on the surface of 316L stainless steel via electrodeposition using PCTM-loaded CPs as building blocks. The chemical composition, morphology and phase of the obtained coating were analyzed using ATR-FTIR, X-ray diffractometer(XRD) and scanning electron microscope(SEM). The results demonstrated that due to the existence of bactericidal cations, PCTM-loaded PPDM coating showed excellent bactericidal function against both Gram negative bacteria E. coli and Gram positive bacteria S. aureus. Moreover, the trigger release of PCTM in coating materials could be realized when glutathione(GSH) existed. When the concentration of GSH was 10 mmol/L, the amount of released PCTM was about 0.9 mg which is three times more than that of released without GSH. Considering the antibacterial and redox-responsive drug releasing property, the PCTM-loaded PPDM coating has a great potential application onto the surface of impalnt metal. Furthermore, the entire strategy may be used in other implantations to creat functional coating to improve the bacterial infection.

Structure and Properties of Brominated Butyl Rubber/Nature Rubber(BIIR/NR) Blends Modified with TBIR^†

ZHANG Jianping, SONG Liyuan, WANG Hao, WANG Riguo, HE Aihua

2018, 39(6): 1334-1341. doi:10.7503/cjcu20170676

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As a new generation of synthetic rubber, trans-1,4-poly(butadiene-co-isoprene) copolymer rubber(TBIR) was used to modify brominated butyl rubber(BIIR)/ nature rubber(NR) blends for high performance inner liner stocks in all steel radial truck tire, and the crosslinking density, filler dispersion, physical and mechanical properties including gas permeability and flexual fatigue resistance of the BIIR/NR/TBIR blends after crosslinking were studied in details. The results indicate that the carbon black filled BIIR/NR/TBIR compounds show increased green strength and modulus with increased TBIR content, and DSC curves prove the crystallizability of TBIR component in the compounds and the crystallization peaks from TBIR can still be detected in the BIIR/NR/TBIR vulcanizates. Blending TBIR with BIIR/NR, the optimum curing time(t₉₀) and the crosslinking density of the compounds slightly reduced. The BIIR/NR/TBIR vulcanizates showed excellent properties, such as improved hot-air aging resistance(10% higher) and air barrier resistance(17% higher), and greatly improved the 1st-class crack resistance(2 to 5 times higher). The mean size of the carbon black aggregates in BIIR/NR vulcanizate after fatigue test became larger than that in BIIR/NR/TBIR vulcanizates. Finally, the structure evaluation of the BIIR/NR/TBIR vulcanizates and its influences in the crack initiation resistance during the dynamic process with periodical stress and strain were discussed in details. TBIR is deemed as an ideal candidate to modify BIIR or BIIR/NR blends for truck tire inner liner stocks with higher crack initiation resistance without deteriorating of other properties.

Sol-gel Preparation of Superhydrophilic Silica Coating-materials with Low Refractive Index^†

ZHANG Shuming, LUO Jianhui, XIA Bibo, LI Yuanyang, HE Meiying, JIANG Bo

2018, 39(6): 1342-1348. doi:10.7503/cjcu20170606

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Porous silica coatings with low refractive index and superhydrophilicity property were prepared via a base-catalysed sol-gel process. Precursor sols were prepared based on a base-catalysed sol-gel process, followed by etching of silica particles in sols with acid fluoride(HF). Then, low refractive index films were prepared by dip-coating process. It was found that the refractive index of coating reduce to 1.101 after etching with 3% HF, the static contact angle of the films reduced to 3° and anti-fogging performance of the coatings is improved significantly.

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