Chemical Research in Chinese Universities

Chemical Research in Chinese Universities Vol.33 No.6 December 2017

2017, 33(6): 0-0.

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Influence of Fluoride Ions on the Structure-directing Effect of Organic Amine in the Synthesis of Aluminophosphate Open-frameworks

TIAN Ye, XU Jun, WANG Zi, DENG Feng, XU Ruren, YAN Wenfu

2017, 33(6): 853-859. doi:10.1007/s40242-017-7131-9

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The crystallization behavior of the initial mixture with the composition of Al₂O₃:4.0P₂O₅:3.0 diethylenetriamine(DETA):xHF:153H₂O was investigated at 180 ℃, where 0 ≤ x ≤ 3. If x ≤ 1.8, three-dimensional open-framework aluminophosphate AlPO-CJ31 was obtained. If 2 ≤ x ≤ 3, a chain-like aluminophosphate(1) was obtained. The crystallization process of both compounds was investigated by means of powder X-ray diffraction(XRD) and the concentrations of Al and P in the liquid product during the crystallization process were analysed by means of inductively coupled plasma atomic emission spectroscopy(ICP-AES). The evolution of the coordination state of Al, P and F during the crystallization was monitored with ²⁷Al, ³¹P and ¹⁹F MAS NMR technique. The influence of the fluoride ions and the source of fluoride ions on the structure-directing effect of DETA was discussed. It was found that the fluoride ions changed the crystallization direction of the initial mixture, i.e., the structure-directing effect of DETA, via altering the distribution or micro-structure of the inorganic fragments.

Synthesis of (Ph₃P)₂PdX₂ Complexes and Their Catalytic Activity for Heck Reaction Involving Aryl Halide and Acrylate

LIU Chengxin, HAN Fangwai, LIU Guiyan, ZHAO Hongkun

2017, 33(6): 860-863. doi:10.1007/s40242-017-7125-7

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Two palladium complexes, (Ph₃P)₂PdBr₂ and (Ph₃P)₂PdI₂, were synthesized by a new method and their structures were confirmed by NMR, elemental analysis and X-ray crystallography. The catalytic activity of the two palladium complexes was evaluated in Mizoroki-Heck cross-coupling reaction of aryl halide with acrylate, and the results show that they all have high catalytic activity to many different substrates.

Structure and Enhanced Antifungal Activity of a Divalent Cobalt(II) Complex with Hexaconazole

ZHOU Jinhua, LI Jingjing, LI Jie, REN Guoyu, REN Yinghui, MA Haixia

2017, 33(6): 864-868. doi:10.1007/s40242-017-7108-8

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A new Co^Ⅱ complex,[CoL₄Cl₂]·2CH₃CH₂OH(L=hexaconazole), was synthesized and characterized by means of elemental analysis, infrared spectroscopy and single-crystal X-ray diffraction. The crystal structural analysis shows that the centrosymmetric Co²⁺ is coordinated by four hexaconazole ligands and two Cl^? to form a distorted octahedral geometry. The complex forms 1D chains through the intermolecular hydrogen bonds interaction of O-H…O and O-H…Cl. Furthermore, the antifungal activities of the complex against Grape anthracnose(I), Botryosphaeria berengriana(Ⅱ), Botryosphaeria ribis(Ⅲ) and Wheat gibberellic(IV) have been investigated and compared with those of the corresponding ligand. The results show that the complex has better antifungal activity than the ligand, which indicates that the coordination of the ligand and the metal enhances the antimicrobialactivity.

Nd_3-xAE_xFe₅O₁₂:Hydrothermal Synthesis, Structure and Magnetic Properties

WU Jie, YUAN Long, WANG Shan, HOU Changmin

2017, 33(6): 869-875. doi:10.1007/s40242-017-7069-y

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Rare-earth ferrite garnet is one of the most important materials applied in microwave transducer and infrared magneto-optical devices, etc. Nd_3?xAE_xFe₅O₁₂(AE=Ca, Sr) crystals, which have cubic structure with the space group of Ia3d and lattice constants over 1.26 nm, were prepared via the mild hydrothermal method. The structural, morhpology and magnetic properties were characterized by means of powder X-ray diffraction, scanning electronic microscopy, as well as vibrating sample magnetometer and Mössbauer spectroscopy, respectively. Mössbauer spectroscopy demonstrates the coexistence of Sr²⁺, Ca²⁺ and Nd³⁺ at the C sites of the dodecahedrons for different substituted garnets. The crystal shape is dodecahedron, and the particle sizes are decreased with increasing the Ca and Sr doping concentrations. By recording the magnetic hysteresis loops and M-T curves at different temperatures, it can be seen that with the increasing x, the saturation magnetization values decrease while the coercive forces increase under the condition of high temperatures.

Preparation of Polyclonal Antibody and Development of a Biotin-streptavidin-based ELISA Method for Detecting Kanamycin in Milk and Honey

SU Ping, CHEN Xiaonan, HE Zhangjing, YANG Yi

2017, 33(6): 876-881. doi:10.1007/s40242-017-7168-9

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Kanamycin is an aminoglycoside antibiotic used increasingly in human and veterinary medicine. However, kanamycin residues in food can cause serious side effects. Here we reported the preparation of polyclonal antibody and the development of an indirect competitive biotin-streptavidin-amplified-based enzyme-linked immunosorbent assay(BA-ELISA) that can sensitively and specifically detect kanamycin residues in milk and honey. The immunogen and coating antigen were synthesized by covalently linking kanamycin to carrier proteins using the carbodiimide method. The anti-kanamycin polyclonal antibodies were obtained from immunized rabbits. The key assay parameters were investigated and optimized. The results show that under optimum conditions, the limit of detection for kanamycin is 0.07 ng/mL and the IC₅₀ is 6.48 ng/mL. Cross-reactivity values of the antibody with four kanamycin analogues are all <1%. Trace amounts of kanamycin in milk and honey samples can be detected by this novel BA-ELISA method successfully with satisfactory recoveries of 91.0%-103.3%. The developed protocol was also validated against liquid chromatography-mass spectrometry, returning a significant correlation. These results indicate that BA-ELISA is a viable option for monitoring kanamycin residues in milk and honey.

Design, Synthesis and Insecticidal Evaluation of Novel N-Pyridylpyrazolecarboxamide Derivatives Containing Isoxazole, Isoxazoline and 1,3,4-Thiadiazole Rings

HUA Xuewen, LIU Chen, ZHOU Sha, CHEN Minggui, XIONG Lixia, LI Yongqiang, LI Zhengming

2017, 33(6): 882-889. doi:10.1007/s40242-017-7147-1

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With the introduction of various heterocyclic rings at the benzene part of anthranilic diamides, a series of N-pyridylpyrazolecarboxamide derivatives containing isoxazole, isoxazoline and 1,3,4-thiadiazole rings was designed, synthesized and evaluated for their insecticidal activities. The structures of the obtained novel target compounds were confirmed by means of ¹H NMR, ¹³C NMR and HRMS. The bioassay results indicated that most of the target compounds displayed moderate or good insecticidal activities against oriental armyworm and diamondback moth at the adopted concentrations compared with chlorantraniliprole, especially compounds Ii and Il, of which the LC₅₀ and LC₉₅ values against oriental armyworm were further measured. The structure-activity relationship demonstrated that the introduction of chlorine in benzene ring, bromomethyl and acetoxyl substituents in 4,5-dihydroisoxazole part was more advantageous to improve the corresponding insecticidal activities than the introduction of other substituents and heterocycles.

Total Synthesis and Biological Evaluation of Wewakazole

LONG Bohua, ZHANG Jingzhao, WANG Xueyan, TANG Xudong, WU Zhengzhi

2017, 33(6): 890-894. doi:10.1007/s40242-017-7129-3

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The total synthesis of Wewakazole was achieved on a gram scale, unambiguously confirming its structure. Three different substituted oxazoles present in this natural product were prepared efficiently. Biological evaluation indicated that Wewakazole significantly inhibited cancer cell proliferation in a dose-dependent manner.

Synthesis and Biological Activity of Imidazo[4,5-c]quinoline Derivatives as PI3K/mTOR Inhibitors

LI Yanjie, ZHANG Xingmin, NIU Shengxiu, ZHAO Yanping, YANG Lijuan, SHAO Xiaowei, WANG Ensi

2017, 33(6): 895-902. doi:10.1007/s40242-017-7074-1

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A series of imidazo[4,5-c]quinoline derivatives(12a-12m) was synthesized with 2-amino-5-bromoben-zoic acid and 4-nitrophenylacetonitrile as starting materials, 6-bromo-4-chloro-3-nitroquinoline as intermediate and Suzuki reaction and closure of the imidazolinone ring with triphosgene as key steps. The structures of the key intermediate and target compounds were confirmed by means of ¹H NMR, ¹³C NMR and HRMS. These compounds show an interesting kinase profile as dual PI3K/mTOR tool compounds.

Double-lipase Catalyzed Synthesis of Kojic Dipalmitate in Organic Solvents

WANG Zhiyuan, LUO Wen, FU Junying, LI Zhibing, WANG Zhongming, LÜ Pengmei

2017, 33(6): 903-907. doi:10.1007/s40242-017-7048-3

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Kojic dipalmitate(KDP) was synthesized by the way of esterification of palmitic and kojic acids in organic solvent, with double-lipase as the biocatalyst. Four commercially available lipases(Amano PS, Novozym 435, Lipozyme TL IM and Lipozyme RM IM) were used to group six double-lipase combinations. These combinations were studied and Amano PS-Novozym 435 was found to have the best efficiency and was selected for optimizing the reaction conditions. The optimal reaction conditions were as follows. The mass ratio of Amano PS to Novozyme 435 was 1:1.5, with stirring speed of 500 r/min, substrates molar ratio of 1:2, 50℃, 5%(mass fraction) catalyst dosage of kojic acid quantity and using acetone as co-solvent. Under these conditions, the diesterification of C5 and C7 hydroxyl groups of kojic acid molecule could be well catalyzed by double-lipase and realize a high KDP yield of 85%.

Effects of ZnO Nanoparticles on Rat Glioma C6 Cells

SU Jing, YU Mingyue, LIN Zhen, ZHAO Hang, LIU Haiyan

2017, 33(6): 908-911. doi:10.1007/s40242-017-7251-2

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Zinc oxide nanoparticles(ZnO NPs) are among the most commonly utilized nanomaterials. They are used in a wide range of applications, including medicine, sunscreens, cosmetics, paints, catalysis, electronics, as well as biosensors, and hence, it is crucial to illustrate their biological effects and risks. In the present study, the effects and mechanism of ZnO NPs(≤ 5 nm) were investigated in rat glioma C6 cells in vitro. The results of transmission electron microscopy(TEM) and X-ray diffraction(XRD) show that ZnO NPs are pure with a uniform diameter of ca. 5 nm. 3-(4,5-Dimethylthiazol-2yl)-2,5-diphenyltetrazolium bromide(MTT) assays on C6 cells show that ZnO NPs, at different concentrations(0-5 μg/mL), can induce significant cytotoxicity in C6 cells in a dose-dependent manner. An increased level of reactive oxygen species(ROS), a decreased level of glutathione(GSH), and an elevated level of glutathione disulfide(GSSG) and the toxicity mechanism are primarily attributed to the induced cellular oxidative stress. 4',6-Diamidino-2-phenylindole(DAPI) staining was used to observe the apoptosis. The results show that C6 cells treated with the ZnO NPs at various concentrations(0, 1.25, 2.5 and 5 μg/mL) can induce apoptosis in a dose-dependent manner. These results suggest that ZnO NPs are the killers of the rat glioma C6 cells, and oxidative stress is the underlying mechanism of this process.

Ultrasonic-assisted Mesoporous Silica Nanoparticle-mediated Exogenous Gene Stable Expression in Tobacco

WANG Zhongni, LIU Huijing, LI Luhua, LI Quanliang, WANG Xiuran, JIANG Yuan, FU Yuqin, LÜ Changli

2017, 33(6): 912-916. doi:10.1007/s40242-017-7240-5

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Although nanotechnology is considered to be one of the most important technologies to promote social and economic development in the twenty-first century, its application in agriculture is relatively few compared with those in other fields. In this article, plasmid carrying GUS gene was successfully delivered into tobacco(Nicotiana tabacum) by mesoporous silica nanoparticles(MSNs) modified with positively charged poly-L-lysine(PLL) with the assist of ultrasonic method. Stable transformation was confirmed by polymerase chain reaction(PCR) detection and GUS histochemical staining. Meanwhile, we also studied the factors that could enhance the genetic transformation efficiency. The result suggests that the callus receptor and a suitable DNA/MSNs ratio contribute a lot to the transformation efficiency. In a word, our research provides an efficient and cost-effective method for gene delivery to plant.

Enhanced Antibacterial Activities of La/Zn-doped BiNbO₄ Nanocomposites

HOU Yanhui, YUAN Huili, CHEN Hang, DING Yan, LI Liangchao

2017, 33(6): 917-923. doi:10.1007/s40242-017-7113-y

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Bi_1?xLa_xNbO₄and Bi_1-xZn_xNbO₄nanocomposites were prepared by a simple coprecipitation method, and their composition, structure and morphology were characterized by modern testing techniques. The antibacterial activities of the as-prepared samples against Staphylococcus aureus, Escherichia coli and Candida albicans were measured by the experiments of powder inhibition zone, inhibition zone diameter and minimum inhibitory concentration under the irradiation of sunlight. The results show that the antibacterial activities of BiNbO₄ doped with La and Zn are superior to that of the parent, and the composition of antibacterial agent and their mass ratio have a great influence on the antibacterial activities. Among these, the antibacterial activity of Bi_0.96La_0.04NbO₄ against three bacteria was best and its antibacterial activity to Candida albicans was better than those to the other two kinds.

Tuning Shell Thickness of MnO/C Core-shell Nanowires for Optimum Performance of Lithium-ion Batteries

ZHANG Dan, LI Guangshe, FAN Jianming, LI Baoyun, LI Liping

2017, 33(6): 924-928. doi:10.1007/s40242-017-7223-6

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MnO/C core-shell nanowires with varying carbon shell thickness were synthesized via calcining resorcinol-formaldehyde resin(RF) with different amounts of hydrothermally synthesized MnO₂ nanowires. The relationship between the carbon shell thickness and the anode performance of the MnO/C materials was discussed. With a suitable carbon shell thickness(6.8 nm), the MnO/C core-shell nanowires exhibit better cycling and rate performance than those with a smaller or larger thickness. The TEM results show that after 50 cycles, the core-shell structure with this thickness can be retained, which leads to superior performance. This contribution provides a significant guiding model for optimizing the electrochemical performance of MnO/C core-shell materials by controlling the thickness of carbon shells.

Physicochemical Properties of Bi-containing Ionic Liquid Analogs Based on Choline Chloride

BU Luxia, LIU Daying, WEI Zhen, MA Zhanlin

2017, 33(6): 929-933. doi:10.1007/s40242-017-7170-2

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The preparation and characterization of homogeneous and colorless ionic liquid analogs(ILAs) containing choline chloride(ChCl), malonic acid and bismuth chloride were investigated. The structure of the above mixture was preliminarily analyzed, and then the physicochemical properties including viscosity, conductivity and density were investigated as functions of temperature and composition. Additionally, the thermal stability of the ILAs and the electrochemical behavior of Bi³⁺ ions in the medium were studied. Structure analysis reveals that the synthesis of deep eutectic solvents(DESs) is closely related to the formation of hydrogen bonds between malonic acid and ChCl, with their viscosity, conductivity and density being greatly dependent on the temperature and composition. Thermogravimetric analysis demonstrates that the ILAs are very stable between room temperature and 398.15 K. And the electrochemical experiments indicate that the bismuth films can be successfully deposited from this ILAs and the deposition mechanism of bismuth is a rather irreversible process. The surface morphology of bismuth films deposited on Cu substrates was very compact and smooth. Thus, ChCl-malonic acid DESs were shown to be a good alternative to aqueous solvents for various deposition-related applications.

Enhanced Visible-light-driven Photocatalytic Performance of In₂O₃-loaded TiO₂ Nanocubes with Exposed (001) Facet

GAO Bifen, WAN Jianfeng, HU Desheng, CHEN Yilin, LIN Bizhou

2017, 33(6): 934-938. doi:10.1007/s40242-017-7133-7

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The heterostructures of In₂O₃ nanoparticle loaded on anatase TiO₂ nanocube with exposed (001) facet (In₂O₃/TiO₂-nanocube) were fabricated via a two-step hydrothermal process. The crystal phase, morphology, micro-structure and photo-absorption property of the products were characterized by FESEM, TEM, XRD, and UV-Vis diffuse reflectance spectroscopy. The results showed that the percentage of exposed (001) facet of TiO₂ nanocube was about 33%. In₂O₃ nanoparticles were successfully decorated on the surface of TiO₂ nanocube to form the In₂O₃/TiO₂ heterojunction. Photocurrent measurements confirmed that (001) faceted surface was advantageous for the charge carrier migration and separation in the composites. In comparison with bare TiO₂ nanocube and In₂O₃/TiO₂-nanoparticle, the In₂O₃/TiO₂-nanocube heterostructures exhibited enhanced activity toward the degradation of rhodamine B and tetracycline under visible light irradiation, which was attributed to the synergic effect of In₂O₃/TiO₂ heterojunction and the exposure of (001) facet.

Preparation of Zinc-nickel-cobalt Ternary Oxide Nanosheets as Electrodes in Supercapacitors

SHI Xue, ZHOU Guowei

2017, 33(6): 939-945. doi:10.1007/s40242-017-7124-8

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Novel zinc-nickel-cobalt ternary oxide nanosheets were successfully synthesized via an easy solvothermal method followed by calcination and were tailored to have different numbers of wrinkles by controlling the volume ratio of the components in the mixed solvent. Nanosheets with more wrinkles yielded a large specific surface area(111.61 m²/g), which improved their electrochemical properties. The resulting products were characterized using a three-electrode system in 6 mol/L KOH electrolyte solution. With unique structures, the nanosheets with more wrinkles displayed a good capacitive behavior and an excellent specific capacitance retention of 97.18% after 2000 continuous charge-discharge cycles. Considering their high electrochemical performance and simple fabrication, we proposed that these unique zinc-nickel-cobalt oxide nanosheets are promising supercapacitor electrodes for energy storage applications.

Rational Design of Ag Nanocubes-Reduced Graphene Oxide Nanocomposites for High-performance Non-enzymatic H₂O₂ Sensing

JI Ye, HAN Tianyi, ZHANG Yong, WANG Ziying, ZHANG Tong, LENG Jiyan

2017, 33(6): 946-950. doi:10.1007/s40242-017-7118-6

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Ag nanocubes-reduced graphene oxide(AgNCs-rGO) nanocomposite was successfully prepared by an in situ synthesis method, in which AgNCs were loaded onto the surface of rGO during the formation of AgNCs in an ethylene glycol solution. Characterization by X-ray diffraction, UV-Vis spectroscopy, and scanning electron microscopy indicated the successful preparation of the AgNCs-rGO nanocomposite. Most importantly, the AgNCs-rGO nanocomposite exhibited excellent electrocatalytic activity for the reduction of H₂O₂, leading to a high-performance non-enzymatic H₂O₂ sensor with a linear detection range and detection limit of approximately 0.1 mmol/L to 70 mmol/L(r=0.999) and 0.58 μmol/L, respectively. Our present work provides a new and highly efficient method for fabricating high-performance electrochemical sensors.

Design of L-Cysteine Functionalized Au@SiO₂@Fe₃O₄/Nitrogen-doped Graphene Nanocomposite and Its Application in Electrochemical Detection of Pb²⁺

NIE Jing, HE Bin, CHENG Yanmei, YIN Wei, HOU Changjun, HUO Danqun, QIAN Linlin, QIN Yunan, FA Huanbao

2017, 33(6): 951-957. doi:10.1007/s40242-017-7101-2

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A novel magnetic electrochemical sensor was designed for determination of lead ions based on gold nanoparticles(AuNPs)@SiO₂@Fe₃O₄/nitrogen-doped graphene(NG) composites functionalized with L-cysteine. The Au@SiO₂@Fe₃O₄/NG was synthesized by the electrostatic adsorption between AuNPs and SiO₂-coated Fe₃O₄NPs(SiO₂@Fe₃O₄) and the amide bond between Au@SiO₂@Fe₃O₄ and NG. L-Cysteine was successfully functionalized on the surface of Au@SiO₂@Fe₃O₄/NGnanocomposites via the S-Au bond between L-cysteine and AuNPs. Owing to numerous active sites in L-cysteines and high conductivity of Au@SiO₂@Fe₃O₄/NG composites, the proposed electrochemical sensor exhibited a well-distributed nanostructure and high responsivity toward Pb(Ⅱ). The sensor linearly responded to Pb²⁺ concentration in the range of 5-80 μg/L with a detection limit of 0.6μg/L, indicating that this L-cysteine functionalized Au@SiO₂@Fe₃O₄/NG composite could be a promising candidate material for the detection of Pb²⁺.

Circular Cationic Compounds B₃Rg_n⁺ of Triangular Ion B₃⁺ Trapping Rare Gases

ZHANG Ruiwen, LI Anyong, LI Zhuozhe

2017, 33(6): 958-964. doi:10.1007/s40242-017-7054-5

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The circular cationic compounds B₃Rg_n⁺(n=1-3, Rg=He-Rn) formed by the electron-deficient aromatic ion B₃⁺ trapping rare gases were studied theoretically. The formed B-Rg bond has large bonding energy in the range of 60-209 kJ/mol, its length is close to the sum of covalent radii of B and Rg, for Ar-Rn. The analyses based on the natural bond orbitals and electron density topology show that the B-Rg bonds for Ar-Rn have strong covalent character. The geometric structures, binding energy, bond nature and thermodynamic stability of the boron-rare gas compounds show that these species for Ar-Rn may be experimentally available. Several different theoretical studies have demonstrated that these triangular cations are aromatic.

Facile Synthesis of Mesoporous Co₃O₄ Nanoflowers for Catalytic Combustion of Ventilation Air Methane

LIU Shankui, LIU Pengcheng, NIU Ruyue, WANG Shuang, LI Jinping

2017, 33(6): 965-970. doi:10.1007/s40242-017-7047-4

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Flower-like Co₃O₄ hierarchical microspheres composed of self-assembled porous nanoplates were prepared by employing Pluronic F127 block-copolymer as template. The samples were characterized by powder X-ray diffraction(PXRD), scanning/transmission electron microscopy(SEM/TEM), and nitrogen adsorption-desorption at 77 K. The results show that the catalytic activity of Co₃O₄ nanoflowers for the combustion of ventilation air methane is higher than that of commercial Co₃O₄. The superior catalytic performance of this material can be related to its dominantly exposed {112} crystal planes and higher content of surface Co³⁺.

Morphology Effect of Metal-organic Framework HKUST-1 as a Catalyst on Benzene Oxidation

LIU Yanfeng, LIU Boliang, ZHOU Qingfeng, ZHANG Tianyong, WU Wubin

2017, 33(6): 971-978. doi:10.1007/s40242-017-6468-4

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An attempt was made to study whether the morphology effect of metal-organic frameworks HKUST-1 could significantly influence the chemical reaction of benzene oxidation. Four representative cupric salts, CuSO₄·5H₂O, Cu(OAc)₂·H₂O, CuCl₂·2H₂O and Cu(NO₃)₂·3H₂O, were treated with 1,3,5-benzenetricarboxylic acid under ultrasound or with static method at room temperature to prepare metal-organic frameworks(12 types of HKUST-1 samples). And the as-prepared HKUST-1 materials were comprehensively investigated by X-ray diffraction, scanning electron microscopy and N₂ adsorption-desorption. The HKUST-1 samples with different morphologies and characterisitcs were employed as catalysts for benzene oxidation with H₂O₂ as oxidant at 60℃ in acetonitrile to achieve the aromatic oxygenates and test their yields. In all the HKUST-1 samples, the HKUST-1/SA, HKUST-1/SA0 and HKUST-1/UN had the higher catalytic activities with the yields of benzene oxygenates of 15.9%, 16.6% and 11.7%, respectively, which can be ascribed to the larger pore volume, the stronger benzene adsorption and the smaller fine crystal particles. Comparatively, the HKUST-1/SN0 and HKUST-1/SC0 with more intact crystal, larger surface area, lower pore volume and weaker benzene adsorption had the lower catalytic activities with the yields of benzene oxygenates not more than 4%. Therefore, our results confirmed that employing various cupric precursors to prepare the HKUST-1 samples with different morphologies and characteristics can be considered as a worth strategy to design many more powerful heterogeneous catalysts.

Thermodynamics on Sulfur Migration in CaSO₄ Oxygen Carrier Reduction by CO

ZHONG Simei, ZHENG Min, PU Sixu, XING Yanbin, LI Kongzhai, WANG Hua

2017, 33(6): 979-985. doi:10.1007/s40242-017-6457-7

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CaSO₄ is an attractive oxygen carrier for chemical looping combustion(CLC) because of its high oxygen capacity and low price. The utilization of a CaSO₄ oxygen carrier suffers the problems of sulfur release, and deactivation caused by sulfur loss. With respect to the fact that partial sulfur release could be recaptured and then recycled to CaSO₄ by CaO sorbent, the mixture of CaSO₄-CaO can be treated as an oxygen carrier. Thermodynamics of CaSO₄ and CaSO₄-CaO reduction by CO have been investigated in this study. The sulfur migrations, including the sulfur migration from CaSO₄ to gas phase, mutual transformation of sulfur-derived gases and sulfur migration from gas phase to solid phase, were focused and elucidated. The results show that the releases of S₂, S₈, COS and CS₂ from CaSO₄ oxygen carrier are spontaneous, while SO₂ can be released at high reaction temperatures above 884℃. SO₂ is the major emission source of sulfur at low CO/CaSO₄ molar ratios, and COS is the major part of the byproducts as soon as the ratio exceeds 4 at 900℃. Under CO atmosphere, all the sulfur-derived gases, SO₂, S₂, S₈ and CS₂, involved are thermodynamically favored to be converted into COS substance, and are spontaneously absorbed and solidified by CaO additive just into CaS species, which may be recycled to CaSO₄ as oxygen carrier in the air reactor. But high reaction temperatures and high CO₂ concentrations are adverse to sulfur capture.

Preparation of Molecularly Imprinted Sericin/Poly(vinyl alcohol) Electrospun Fibers for Selective Removal of Methylene Blue

ZHAO Rui, LI Xiang, SUN Bolun, LI Yumei, LI Yanzi, WANG Ce

2017, 33(6): 986-994. doi:10.1007/s40242-017-7115-9

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Sericin(SS), as an abundant and renewable resource in nature, has been proven to be a good adsorbent for metal ions or organic dyes removal. In this study, glutaraldehyde vapor cross-linked sericin-based electrospun fiber adsorbent was developed for the removal of methylene blue(MB) from wastewater. To overcome the problem of decreasing adsorption capacity by excessive functional group cross-linking, MB-imprinted sericin/poly(vinyl alcohol) (PVA) electrospun fiber adsorbent was prepared. Biocompatible PVA was added to the electrospinning solution to improve the spinnability and mechanical property. Scanning electron microscopy(SEM), Fourier transforms infrared spectroscopy(FTIR), and so forth were used to confirm their structures and composition. The adsorption performance toward the template molecule MB, including pH effect, adsorption isotherm, adsorption kinetics, adsorption selectivity, and reusability, was investigated. By comparison with non-imprinted sericin/PVA electrospun fibers, MB-imprinted sericin/PVA electrospun fiber adsorbent showed an enhanced and selective adsorption capacity toward MB with a good regeneration and recycling ability. The adsorption test suggests that the resulting MB-imprinted sericin/PVA electrospun fibers are promising adsorbents for MB removal from aqueous system.

PVA/PEG Hybrid Hydrogels Prepared by Freeze-thawing and High Energy Electron Beam Irradiation

ZHAO Chunming, LU Xueting, HU Qianqian, LIU Shuai, GUAN Shuang

2017, 33(6): 995-999. doi:10.1007/s40242-017-7107-9

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In this paper, poly(vinyl alcohol)(PVA) and PVA/poly(ethylene glycol)(PEG) hybrid hydrogels were synthesized by freeze-thawing or freeze-thawing followed by high energy electron beam irradiation. The influence of PEG molecular weight, mass ratios of PVA to PEG, thawing temperature and number of freeze-thawing(FT) cycles on the mechanical strength of PVA/PEG hydrogel was investigated. Also, the thermal behaviors were examined by differential scanning calorimetry(DSC) and the microstructures were observed with scanning electron microscopy(SEM). The results suggest that the addition of PEG improves the mechanical strength of PVA hydrogel and the irradiation reduces both the strength of PVA/PEG hydrogel slightly and the degree of crystallinity. The improved properties suggest that PVA/PEG hydrogel can be a good candidate for the application in the biomedical.

Moisture Absorption and Mechanical Properties of Chemically Modified Linen/Polypropylene Composites

HU Qiuxue, LI Li, YAN Wenling, ZHAO Qi, ZHANG Niaona, ZHANG Yumei, DONG Jinbiao, LIU Baijun, HU Wei

2017, 33(6): 1000-1006. doi:10.1007/s40242-017-7097-7

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To decrease the moisture absorption and improve the mechanical properties of linen/polypropylene(PP) composites, linen was modified with silane N-[3-(trimethoxysilyl) propyl]ethylenediamine(AAPTS), surfactant trimethyloctadecylammonium bromide(STAB), and both AAPTS and STAB, respectively. Fourier transform infrared(FTIR) spectra showed that the linen was successfully modified and alkyl chains were attached through different treatments. The linen and PP were compounded by melt compressing. The moisture absorption of linen was decreased after STAB and AAPTS-STAB modifications. The moisture absorption, mechanical property and thermal property of the composites were also characterized. The results show that the moisture absorption of the AAPTS-modified linen(F1) reinforced PP(PPF1) is 8.09%, which is higher than that of the unmodified linen reinforced PP(PPF)(7.89%). The moisture absorption of the STAB-AAPTS-modified linen(F3) reinforced PP(PPF3) is 6.58%. The tensile strengths of PPF1 and PPF3 are 33.7 and 35.8 MPa, which are improved by 22.5% and 30% compared with that of PPF(27.5 MPa), respectively. Nevertheless, the moisture absorption of the STAB-modified linen(F2) reinforced PP(PPF2) is decreased by 22.4%, and the tensile strength is improved by 30% compared with those of PPF. Scanning electron microscopy(SEM) analysis of the fractured surface confirms the good interfacial adhesion of PPF2 compared with those of other composites. Furthermore, the 5% mass loss temperatures of the composites are all higher than 290℃. Thus, linen modified with STAB is a promising reinforcement for biocomposites.

Mechanical and Thermal Properties of Waterborne Polyurethane Films Modified by CaCO₃@TiO₂ Particles with UV Absorption Activity

JIANG Tiechao, FAN Qingqiu, HUANG Chunying, LI Zhen, GUO Lijie, ZHOU Bing

2017, 33(6): 1007-1011. doi:10.1007/s40242-017-7088-8

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CaCO₃@TiO₂ particles were synthesized through a direct carbonation method, which can be used as the substitutes of TiO₂ in pigments and coatings. To improve the dispersion in waterborne polyurethane(WPU) suspensions, CaCO₃@TiO₂ particles were modified by stearic acid. SEM tests of the fractured surfaces of the composites films showed that the CaCO₃@TiO₂particles were well embedded in the WPU matrix. And the mechanical properties, thermal stability and water resistance of the composites films were improved by the introduction of CaCO₃@TiO₂ particles.

Preparation of β-Cyclodextrin/Fe₃O₄/Polyvinylpyrrolidone Composite Magnetic Microspheres for the Adsorption of Methyl Orange

SI Qingbo, WEN Qian, YANG Qingbiao, SONG Yan, LI Yaoxian

2017, 33(6): 1012-1016. doi:10.1007/s40242-017-7083-0

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Magnetic microspherical β-cyclodextrin(CD)/Fe₃O₄@polyvinylpyrrolidone(PVP) particles, in which embedded Fe₃O₄ particles were coated by β-CD/glutaraldehyde crosslinked PVP, were synthesized via electrostatic spray and thermal crosslinking technologies. The magnetic microspheres were characterized by infrared spectroscopy, X-ray diffraction, scanning electron microscopy(SEM) and magnetic measurements, and the adsorption performance of the β-CD/Fe₃O₄@PVP composite nanoparticles for methyl orange was studied. The results show that the β-CD/Fe₃O₄@PVP microspheres could be quickly separated from the adsorption system under an external magnetic field within 30 s and that the adsorption capacity of the microspheres for methyl orange reaches greater than 90%, with a maximum adsorption quantity of 47.62 mg/g.

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