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2016 Vol.32 No.6
 Published: 01 December 2016

Contents | | Letter | Articles |
 
 
 
Contents
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Chemical Research in Chinese Universities Vol.32 No.6 August 2016
2016 Vol. 32 (6): 0-0 [Abstract] ( 1 ) [HTML 1KB] [PDF 1206KB] ( 12 )   
doi:

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Chemical Research in Chinese Universities Vol.32 No.1-6 December 2016
2016 Vol. 32 (6): 1-8 [Abstract] ( 1 ) [HTML 1KB] [PDF 247KB] ( 2 )   
doi:

Letter
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YAN Luomei, ZHOU Hua, WU Cunqi, WANG Lidan, YANG Wei, JIN Manyu, ZHAO Yongxia, XU Jingwei
A pH Sensitive Fluorescence Probe Based on Tricarbocyanine
2016 Vol. 32 (6): 877-881 [Abstract] ( 4 ) [HTML 1KB] [PDF 0KB] ( 10 )   
doi: 10.1007/s40242-016-6213-4

A pH sensitive near-infrared (NIR) fluorescent probe, IR-DO3A, was synthesized. It was based on combination of tricarbocyanine that had typical NIR absorption and fluorescent emission spectrum, and DO3A (1,4,7,10-tetra azacyclododecane -1,4,7-triyl)triacetic acid) that had three side chain of carboxylic acids. Phenyl sulfonamide that was used to maintain the density of electronic cloud of tricarbocyanine backbone and improve the solubility of the whole molecule was selected to connect tricarbocyanine and DO3A by several substitution reactions under some certain conditions. The final product, IR-DO3A was confirmed by NMR and MS spectrums, and had a better solubility in polar solvent than tricarbocyanine. The optical properties of IR-DO3A in two mixture solvents were studied. It had maximum Uv-vis absorption at 750nm and 805nm, fluorescent emission at 808nm, all these wavelengths were in NIR range and there was a 58nm Stokes-Shift. Also its optical properties at different pH in water were studied and it was sensitive in pH 6~9, which related with the protonation and deprotonation processes of IR-DO3A at different pH. These pH sensitive and NIR-fluorescent properties may result in an application for revealing the pH changes of physiological diseases.

Articles
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SUN Dandan, CAO Yanyan, XU Yanyan, ZHANG Guoying, SUN Yaqiu
Tunable Synthesis of Core-shell α-Fe2O3/TiO2 Composite Nanoparticles and Their Visible-light Photocatalytic Activity
2016 Vol. 32 (6): 882-888 [Abstract] ( 6 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-016-6252-x

Uniform α-Fe2O3/amorphous TiO2 core-shell nanocomposites were prepared via a hydrolysis method and α-Fe2O3/anatase TiO2 core-shell nanocomposites were obtained via a post-calcination process. The structure and morphology of the products were characterized by powder X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and scanning electron microscopy. Amorphous TiO2 nanoparticles with diameters of ten to several tens nanometer were formed on the surface of α-Fe2O3 nanoparticles and the coverage density of the secondary TiO2 nanoparticles in the composite can be controlled by varying the concentration of Ti(BuO)4 in the ethanol solution. The visible-light photocatalytic properties of different products towards Rhodamine B(RhB) were investigated. The results show that the α-Fe2O3/amorphous TiO2 exhibits a good photocatalytic property owing to the extension of the light response range to visible light and the efficient separation of photogenerated electrons and holes between α-Fe2O3 and amorphous TiO2.

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HOU Xuemei, ZHAO Changjie, TIAN Yanlong, DOU Shuliang, ZHANG Xiang, ZHAO Jiupeng
Preparation of Functionalized Fe3O4@SiO2 Magnetic Nanoparticles for Monoclonal Antibody Purification
2016 Vol. 32 (6): 889-894 [Abstract] ( 9 ) [HTML 1KB] [PDF 0KB] ( 7 )   
doi: 10.1007/s40242-016-6251-y

Magnetic Fe3O4@SiO2 nanoparticles with superparamagnetic properties were prepared via a reverse mi-croemulsion method at room temperature. The as-prepared samples were characterized by transmission electron mi-croscopy(TEM), X-ray diffractometry(XRD), and vibrating sample magnetometry(VSM). The Fe3O4@SiO2 nanoparticles were modified by (3-aminopropyl)triethoxysilane(APTES) and subsequently activated by glutaraldehyde(Glu). Protein A was successfully immobilized covalently onto the Glu activated Fe3O4@SiO2 nanoparticles. The adsorption capacity of the nanoparticles was determined on an ultraviolet spectrophotometer(UV) and approximately up to 203 mg/g of protein A could be uniformly immobilized onto the modified Fe3O4@SiO2 magnetic beads. The core-shell of the Fe3O4@SiO2 magnetic beads decorated with protein A showed a good binding capacity for the chime-ric anti-EGFR monoclonal antibody(anti-EGFR mAb). The purity of the anti-EGFR mAb was analyzed by virtue of HPLC. The protein A immobilized affinity beads provided a purity of about 95.4%.

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CHEN Yanli, FENG Lai
Synthesis, Characterization and Control of Proportion of Polymorph C in ITQ-16 and ITQ-17 Films
2016 Vol. 32 (6): 895-901 [Abstract] ( 18 ) [HTML 1KB] [PDF 0KB] ( 6 )   
doi: 10.1007/s40242-016-6126-2

Continuous ITQ-16 and ITQ-17 films on silicon wafer were prepared in fluoride media using TEAOH as organic structure-directing agent. The proportion of polymorph C in the as-synthesized ITQ-16 and ITQ-17 films was determined via X-ray diffraction characterization. The proportion of polymorph C in the ITQ-16 and ITQ-17 films was controlled via optimizing the compositions of the reaction mixtures and reaction conditions, such as varying the Si/Ge molar ratio and adding n-propyl alcohol as a solvent in the reaction mixture. The Ge atoms in the reaction media strongly increased the crystallization of polymorph C in ITQ-16 and ITQ-17 films. Moreover, the stabilizing and buffering effect of n-propyl alcohol on crystal growth further enhanced the proportion of polymorph C in the ITQ-16 and ITQ-17 films. For potential catalytic applications, Al was incorporated into the framework of polymorph C, and a pure phase of polymorph C in Al-ITQ-17 film was achieved from the synthesis gel in the n-propyl alcohol phase.

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GHORBEL Khouloud, LITAIEM Hajer, KTARI Lilia, GARCIA-GRANDA Santiago, DAMMAK Mohamed
Synthesis, Structural Study and Phase Transitions Characterization by Thermal Analysis and Vibrational Spectroscopy of an Ammonium Rubidium Arsenate Tellurate
2016 Vol. 32 (6): 902-911 [Abstract] ( 15 ) [HTML 1KB] [PDF 0KB] ( 16 )   
doi: 10.1007/s40242-016-6056-z

The Rb2.42(NH4)0.58(HAsO4)(H2AsO4)·Te(OH)6 crystals(denoted by RbNAsTe) crystallize in the monoclinic system, space group P21/n with the following parameters:a=1.3059(5) nm, b=0.6755(3) nm, c=1.6675(6) nm, β=94.126(4)°, Z=4 and V=1.46733(10) nm3. Thermal analyses(DSC, DTA and TG) confirm the presence of the phase transition and the temperature of the decomposition. The vibrational spectroscopy study at room temperature show the presence and the independence of anionic groups, cationic groups, and give more importance to the hydrogen bonds. Raman spectra were recorded in the temperature range of 298-503 K. The temperature dependence of the Raman line shift, intensity reduction and the half width detects the phase transitions and confirms their nature. So, the phase transition at 453 K corresponds to the superprotonic-ionic conduction phase transition, and those at 483 and 491 K correspond to the decomposition of our material.

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WANG Cuicui, CAI Wensheng, SHAO Xueguang
Determination of Cysteine Using Near-infrared Diffuse Reflectance Spectroscopy with Enrichment via Thiol-maleimide Click Reaction
2016 Vol. 32 (6): 912-916 [Abstract] ( 11 ) [HTML 1KB] [PDF 0KB] ( 12 )   
doi: 10.1007/s40242-016-6279-z

Enrichment technique has been proved to be an efficient way to make the near-infrared diffuse reflectance spectroscopy(NIRDRS) suitable for micro analysis. However, low selectivity presented by conventional enrichment methods makes the quantitative analysis easy to be affected by the coexisting components. In this study, a specific enrichment method with chemical bonding via thiol-maleimide click reaction was used to achieve the reduction of the interferences. Taking cysteine as the analyzing target, maleimide-functionalized SiO2 nanoparticles were prepared for the enrichment of cysteine. Then determination of cysteine in aqueous solution and human serum was studied using the partial least squares model built from the NIRDRS spectra of the adsorbate. The results show that the concentration that can be quantitatively detected is as low as 2.0 μg/mL, and the correlation coefficient(R) between the reference and predicted concentration is 0.9871 for the validation samples. The recoveries are in the range of 89.5%-113.8% for human serum samples in the concentration range of 0-16.2 μg/mL.

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FANG Xiaoxing, ZHENG Ji, YAN Guiqin
A Convenient “Turn On-off” Phosphorescent Nanosensor for Detection of Biotin Based on Quantum Dots/CTAB
2016 Vol. 32 (6): 917-923 [Abstract] ( 22 ) [HTML 1KB] [PDF 0KB] ( 22 )   
doi: 10.1007/s40242-016-6219-y

A switchable room-temperature phosphorescence(RTP) nanosensor based on an MPA-capped Mn-doped ZnS QDs/CTAB composite system(MPA=3-mercaptopropionic acid; CTAB=cetyltrimethyl ammonium bromide; QDs=quantum dots) was established for the detection of biotin. The phosphorescence intensity of QDs/CTAB could be regularly quenched with the increase of biotin. Under optimal conditions, this method yielded two linear ranges of 2-20 μg/L and 20-140 μg/L with respective correlation coefficients of 0.993 and 0.990, as well as a detection limit of 0.93 μg/L. Therefore, the analytical potential of the proposed nanosensor was evaluated by detecting biotin in urine and biotin tablets. This approach yielded satisfactory results because of the effective elimination of background fluorescence and light scattering from the sample matrix. This approach provides a practical method for biotin detection.

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QI Pengjia, WANG Ziying, WANG Rui, XU Yinan, ZHANG Tong
Studies on QCM-type NO2 Gas Sensor Based on Graphene Composites at Room Temperature
2016 Vol. 32 (6): 924-928 [Abstract] ( 10 ) [HTML 1KB] [PDF 0KB] ( 12 )   
doi: 10.1007/s40242-016-6129-z

Synthetic graphene composite was modified on a transducer of quartz crystal microbalance(QCM) to fabricate a gas sensor for low concentration nitrogen dioxide(NO2) detection. The gas sensing properties of the QCM coated with SnO2-rGO and AgNPs-SnO2-rGO composites were investigated when exposing QCM to low NO2 con-centration(2.05-20.5 mg/m3) atmosphere at room temperature. The sensing performances of the QCM with AgNPs-SnO2-rGO composites were enhanced by the introduction of Ag nanoparticles, and the QCM modified with AgNPs-SnO2-rGO composites could detect NO2 at room temperature.

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LI Hongshuang, WANG Xinran, DUAN Guiyun, XIA Chengcai, XIAO Yuliang, LI Furong, GE Yanqing, YOU Guirong, HAN Junfen, FU Xiaopan, TAN Shanhui, WANG Rongwei
Synthesis, Antitumor Activity and Preliminary Structure-activity Relationship of 2-Aminothiazole Derivatives
2016 Vol. 32 (6): 929-937 [Abstract] ( 3 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-016-6304-2

In this paper, we described the synthesis of 2-aminothiazole sublibrary containing methyl, bromo, phenyl or butylidene at 4- or/and 5-position of its core. All target compounds were evaluated for their antitumor activities against human lung cancer cell line H1299 and human glioma cell line SHG-44. Among the compounds screened, 4,5,6,7-tetrahydrobenzo[d]thiazole(26b) exhibited the most potent antitumor activities with IC50 values of 4.89 and 4.03 μmol/L against the two tested cell lines, respectively. Preliminary structure-activity relationship(SAR) studies of these compound were subsequently investigated.

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LI Fengran, LIU Yang, WANG Shuai, WEI Gaofei, CHENG Maosheng
Synthesis and Tumor Cytotoxicity of Novel 1, 2, 3-Triazole-substituted 3-Oxo-oleanolic Acid Derivatives
2016 Vol. 32 (6): 938-942 [Abstract] ( 13 ) [HTML 1KB] [PDF 0KB] ( 7 )   
doi: 10.1007/s40242-016-6301-5

Fifteen novel 3-oxo-oleanolic acid esters bearing aryl substituted 1,2,3-triazolyl methyl moiety were synthesized via the method of Copper(I)-catalyzed Huisgen cycloaddition. The cytotoxicity evaluation results of these compounds against five human tumor cell lines show that most of these compounds presented potent activity and selectivity against A375-S2 and HT1080 cells. Compound 6c, with a p-NO2 at the bezene ring, possesses the best inhibitory activity against A375-S2(IC50=2.82 μmol/L) and HT1080(IC50=1.69 μmol/L).

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LI Min, JIN Yongri, WANG Xiaozhong, WU Qian, LIU Ying, LI Peng, LI Xuwen
Studies on Triterpenoid Glycosides from Rhizomes of Panacis majoris and Their Antiplatelet Aggregation Activity
2016 Vol. 32 (6): 943-946 [Abstract] ( 8 ) [HTML 1KB] [PDF 0KB] ( 6 )   
doi: 10.1007/s40242-016-6285-0

A new triterpenoid glycoside(1) and seven known triterpenoid glycosides, pseudoginsenoside RT2(2), yesanchinoside R2(3), vinaginsenoside R13(4), vinaginsenoside R8(5), notoginsenoside E(6), 6'''-O-acetylginsenoside Re(7), 6"-O-acetylginsenoside Rb1(8), were isolated from the rhizomes of Panacis majoris. The new triterpenoid glycoside was elucidated as 3-O-[β-D-glucopyranosyl-(1→2)-β-D-(6'-O-ethyl)-glucuronopyranosyl]-oleanolic acid-28-O-β-D-glucopyranoside by extensive spectroscopic and phytochemical methods. Compounds 2-8 were obtained from the plant for the first time. Compounds 3 and 4 displayed good activities against adenosine diphosphate (ADP)-induced platelet aggregation, and compounds 1, 5, 6 and 8 showed moderate activities. Compound 6 exhibited moderate antiplatelet aggregation activity induced by arachidonic acid(AA).

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SHEN Guodong, ZHAO Lingyu, BAO Weiliang
1, 1'-Binaphthyl-2, 2'-diamine Dihydrochloride: an Efficient Ligand for the N-Arylation of Imidazole with Aryl/heteroaryl Halides Catalyzed by CuI
2016 Vol. 32 (6): 947-951 [Abstract] ( 6 ) [HTML 1KB] [PDF 0KB] ( 11 )   
doi: 10.1007/s40242-016-6263-7

Employing 1,1'-binaphthyl-2,2'-diamine(BINAM) dihydrochloride as an efficient and commercially available ligand, relatively mild and highly efficient copper-catalyzed coupling reactions of imidazole with aryl and heteroaryl halides have been developed. Various N-arylimidazoles could be synthesized in moderate to excellent yields.

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LIU Yang, LIU Ming, ZHANG Dongkai, HUA Xuewen, WANG Baolei, ZHOU Sha, LI Zhengming
Design, Synthesis and Fungicidal Activity of Novel Strobilurin-1, 2, 4-Triazole Derivatives Containing Furan or Thiophene Rings
2016 Vol. 32 (6): 952-958 [Abstract] ( 6 ) [HTML 1KB] [PDF 0KB] ( 12 )   
doi: 10.1007/s40242-016-6253-9

A series of strobilurin-1,2,4-triazole derivatives containing a furan or thiophen ring was designed and synthesized. The structures of the compounds were characterized by 1H NMR, 13C NMR and HRMS spectra. The bi-oassays indicated that the fungicidal activities of compounds 10b(EC50=14.82 mg/L) and 10c(EC50=18.72 mg/L) against Cercospora arachidicola Hori in vitro were much higher than that of Azoxystrobin as control(EC50=40.54 mg/L) and the fungicidal activities of compounds 10u(EC50=8.66 mg/L) and 10n(EC50=9.89 mg/L) against Rhizotonia cerealis in vitro were higher than that of the same control(EC50=10.86 mg/L). Compounds 10b, 10c, 10n and 10k could be considered as the leading compounds for further investigation.

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ZHOU Yan, LI Renjun, WANG Xiaolong, HE Ling, GUAN Mei, WU Yong
Facile Synthesis of Unsymmetrical N-Aryl-2, 2-di(1H-indol-3-yl) Acetamide Derivatives
2016 Vol. 32 (6): 959-966 [Abstract] ( 0 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-016-6233-0

A facile and highly efficient method has been developed for the synthesis of unsymmetrical N-aryl-2,2-di(1H-indol-3-yl)acetamide derivatives by regioselective Friedel-Crafts alkylation of the N-aryl-2-hydroxy-2-(1H-indol-3-yl) acetamide derivatives with various indoles catalyzed by 2 mol/L H2SO4 at room temperature in a short reaction time, the yield was up to 94%.

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Farag A. El-Essawy, Nader M. Boshta, Ayman K. El-Sawaf, Amal A. Nassar, Mohamed S. Khalafallah
Synthesis of Novel 3-Substituted Pyridothienopyrimidine Derivatives with Biological Evaluation as Antimicrobial Agents
2016 Vol. 32 (6): 967-972 [Abstract] ( 9 ) [HTML 1KB] [PDF 0KB] ( 13 )   
doi: 10.1007/s40242-016-6218-z

Novel 3-substituted pyridothienopyrimidine derivatives have been synthesized via the reaction of 2-{7,9-dimethyl-4-oxopyrido[3',2':4,5]thieno[3,2-d]pyrimidin-3(4H)-yl}acetohydrazide(5) with a variety of active reagents and chemicals. Structures of the newly synthesized compounds were established based on spectral data. The resulting pyridothienopyrimidine derivatives were evaluated for their possible antimicrobial activity and some of them represent a new class of potentially antimicrobial compounds, especially compounds 9 and 18 which displayed the highest activity against Gram-positive bacteria, Gram-negative bacteria, and Fungi in MIC range of 0.12-1.95 μg/mL.

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YANG Haoran, REN Yujie, GAO Xiaodong, GAO Yonghong
Synthesis and Anticoagulant Bioactivity Evaluation of 1, 2, 5-Trisubstituted Benzimidazole Fluorinated Derivatives
2016 Vol. 32 (6): 973-978 [Abstract] ( 13 ) [HTML 1KB] [PDF 0KB] ( 10 )   
doi: 10.1007/s40242-016-6205-4

Some 1,2,5-trisubstituted benzimidazole fluorinated derivatives were designed and screened by molecular docking. Five compounds which obtained high scores were selected to synthesize. All the target products were char-acterized by 1H NMR, 13C NMR and high resolution mass spectra(HRMS) and preliminarily screened for inhibitory activity against thrombin, among which three compounds(5a, 5c and 5e) were evaluated in vitro. The results showed that compounds 5a, 5c and 5e exhibited better anticoagulant activity than argatroban. Docking simulations demonstrated that these compounds may act as candidates for further studies on thrombin inhibitors.

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WU Jie, LIU Huanhuan, YUAN Long, HOU Changmin
Improved Energy Conversion Efficiency of ZnO/Polythiophene Solar Cell in Ga-Doped ZnO Nanorod Array Photoanode
2016 Vol. 32 (6): 979-984 [Abstract] ( 11 ) [HTML 1KB] [PDF 0KB] ( 2 )   
doi: 10.1007/s40242-016-6195-2

We reported the fabrication and doping effect of Ga-doped ZnO nanorods/electropolymerized polythio-phene(e-PT) hybrid photovoltaic(h-PV) devices. Ga-Doped ZnO nanorod array photoanode devices were fabricated via hydrothermally growing nanorods on sol-gel spin-coating ZnO seed layer, and then the nanorod array was immersed into a thiophene solution to yield a thin polythiophene film by electrochemically polymerization. Afterwards, a thin layer of Al was deposited on the surface of polythiophene to make an electrode for photovoltaic measurement. The ZnO nanorods with different Ga-doping contents were characterized by means of X-ray diffraction(XRD), scanning electron micrograph(SEM) and X-ray photoelectron spectroscopy(XPS). Photovoltaic J-V characterization was performed on the e-PT/ZnO bilayer and bulk heterojunction(BHJ) devices. Though the unsubstituted polythiophene is not an ideal polymer material for solar cells with high power conversion efficiency, it is a sound model for the study on the effect of dopant in hybrid materials. The results indicate that doping Ga can substantially improve the power conversion efficiency of the ZnO-polythiophene solar cell.

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GAO Xinyu, MA Junxiu, RUAN Fangqi, ZHANG Tianlong, LI Hua
In situ ATR-FTIR Combined with SIMPLISMA Algorithm to Investigate the Synthesis Mechanism of 4-Amino-3, 5-dimethyl Pyrazole
2016 Vol. 32 (6): 985-991 [Abstract] ( 7 ) [HTML 1KB] [PDF 0KB] ( 11 )   
doi: 10.1007/s40242-016-6189-0

In situ attenuated total refletion-Fourier transform infrared spectroscopy(ATR-FTIR) was used to monitor and acquire spectral information on the synthesis of 4-amino-3,5-dimethyl pyrazole. Principal component analysis(PCA) was used to determine the number of principle components(PCs). The score vectors of the PCs were analysed using the simple-to-use interactive self-modelling mixture analysis(SIMPLISMA) algorithm to obtain spectral and concentration profiles for the reactants, intermediates and product. The vibrational frequencies of the interme-diates were calculated via density functional theory(DFT) at the level of the B3LYP/6-311++G(d,p) basis set, and the geometrical configurations of the intermediates were simultaneously optimized. Finally, a reasonable synthesis mechanism for 4-amino-3,5-dimethyl pyrazole was determined based on the changes observed in the feature peaks. The results from the SIMPLISMA algorithm correlated well with the quantum chemistry calculations. This proved that the SIMPLISMA algorithm combined with ATR-FTIR can be used to determine the synthesis mechanism for 4-amino-3,5-dimethyl pyrazole and can even provide a new, useful method to explore dynamic synthesis reaction mechanisms.

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LIU Lihong, WANG Chunfeng, ZHUO Kelei
Cetyltrimethylammonium Bromide(CTAB)-Ionic Liquid Composite Modified Electrode for Sensitive Cyclic Voltammetric Determination of Bisphenol A
2016 Vol. 32 (6): 992-995 [Abstract] ( 16 ) [HTML 1KB] [PDF 0KB] ( 12 )   
doi: 10.1007/s40242-016-6162-y

A sensitive electrochemical sensor for determining bisphenol A(BPA) was designed. The sensor was a glassy carbon electrode modified with the surfactant cetyltrimethylammonium bromide and the ionic liquid 1-decyl-3-methylimidazolium tetrafluoroborate. The ability of the new sensor to measure BPA was investigated in cyclic voltammetry experiments. Under optimized conditions, the sensor gave a linear response range for BPA of 2.19×10-7-3.28×10-5 mol/L and a detection limit of 7.31×10-8 mol/L(S/N=3). BPA could be determined with a lower detection limit, a wider linear range, and more sensitivity using the sensor than using other electrochemical sensors or high performance liquid chromatography with UV detection. The new sensor was used to determine BPA in tap water with recoveries of 97.5%-98.7% and a relative standard deviation <2.9%. The results show that the sensor can be used to determine trace BPA concentrations in tap water.

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LIANG Dongmei, LENG Xia, MA Yuchen
Electronic and Optical Properties of B-and/or In-Doped GaAs Calculated Using Many-body Green's Function Theory
2016 Vol. 32 (6): 996-1004 [Abstract] ( 19 ) [HTML 1KB] [PDF 0KB] ( 8 )   
doi: 10.1007/s40242-016-6144-0

Using ab initio many-body Green's Function theory, the electronic and optical properties of pure BAs, InAs as well as B-and/or In-doped GaAs supercells were studied. The results show that the calculated quasiparticle band gaps of BAs and InAs are in agreement with the experiments. The electronic and optical absorption properties of B-and/or In-doped GaAs are very sensitive to the lattice constant models used in the calculations, which can explain the controversies in previous theoretical and experimental works. Under the lattice constant condition based on the Vegard's Law, the reduced band gap and the redshift of the first excited state E0 can be observed for InyGa1-yAs with In concentrations(atomic fractions) ranging from 0 to 15.625%, while the band gap increase and the blueshift of state E0 can be realized for BxGa1-xAs. However, an opposite trend can be found when the lattice constant is fixed to the experimental value, i.e., In doping leads to a band gap increase and a blueshift of the E0 state, while B doping results in a band gap decrease and a redshift of the E0 state. For BxGa1-x-yInyAs, the values of the band gap variation and the shift of state E0 are well located between the B and In mono-doping cases. It is worth mentioning that B doping does not introduce new impurity states in the band gap of GaAs or InyGa1-yAs.

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BEN Shunge, YUAN Fulong, ZHU Yujun
Effect of Zr Addition on Catalytic Performance of Cu-Zn-Al Oxides for CO2 Hydrogenation to Methanol
2016 Vol. 32 (6): 1005-1009 [Abstract] ( 14 ) [HTML 1KB] [PDF 0KB] ( 11 )   
doi: 10.1007/s40242-016-6130-6

A series of 50%CuO-25%ZnO-25%Al(Zr) oxide catalysts was synthesized by a reverse co-precipitation method and characterized by XRD, N2 adsorption-desorption, H2-TPR, H2-TPD and CO2-TPD, and used as catalyst for CO2 hydrogenation to methanol under mild conditions(200-260℃ and 1-3 MPa). Consequently, H2-TPR exhibited that the dispersed CuO species increased with the zirconium content, while the H2-TPD showed that small amount of zirconia can increase the H2 desorption amount. As a result, Cat-2 and Cat-3 exhibited an enhanced H2-spillover effect, the most H2 desorption amount, which showed an optimum activity of about 7% methanol yield.

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LI Qingyan, LIU Zhou, HUANG Lingyan, TENG Jiuwei, BAI Yan
Characterization and Mechanism Elucidation of Dye Adsorption Using Cuprous Selenide Nanoparticles from Aqueous Solutions
2016 Vol. 32 (6): 1010-1015 [Abstract] ( 22 ) [HTML 1KB] [PDF 0KB] ( 13 )   
doi: 10.1007/s40242-016-6116-4

The removal of cationic dyes, methylene blue(MB) and rhodamine B(RB), and anionic dyes, methyl or-ange(MO) and eosin Y(EY), from aqueous solutions by adsorption using Cu2Se nanoparticles(Cu2SeNPs) was studied. The effects of the initial pH values, adsorbent doses, contact time, initial dye concentrations, salt concentrations, and operation temperatures on the adsorption capacities were investigated. The adsorption process was better fitted the Langmuir equation and pseudo-second-order kinetic model, and was spontaneous and endothermic as well. The adsorption mechanism was probably based on the electrostatic interactions and π-π interactions between Cu2SeNPs and dyes. For an adsorbent of 0.4 g/L of Cu2SeNPs, the adsorption capacities of 23.1(MB), 22.9(RB) and 23.9(EY) mg/g were achieved, respectively, with an initial dye concentration of 10 mg/g(pH=8 for MB and pH=4 for RB and EY) and a contact time of 120 min. The removal rate of MB was still 70.4% for Cu2SeNPs being reused in the 5th cycle. Furthermore, the recycled Cu2SeNPs produced from selenium nanoparticles adsorbing copper were also an effective adsorbent for the removal of dyes. Cu2SeNPs showed great potential as a new adsorbent for dyes removal due to its good stability, functionalization and reusability.

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ZHANG Xuena, ZHONG Xinwen, YANG Zhe, SONG Jiapeng, LU Haiyan
Carbon-covered Tungsten Carbide Nanoparticles: Solid-state Synthesis and Application as Stable Electrocatalysts for the Hydrogen Evolution Reaction
2016 Vol. 32 (6): 1016-1018 [Abstract] ( 23 ) [HTML 1KB] [PDF 0KB] ( 13 )   
doi: 10.1007/s40242-016-6107-5

Carbon-covered tungsten carbide nanoparticles(cc-WCNPs) were prepared via a one-step solid-state reaction between W(CO)6 and triphenylamine at 850℃ under a sealed Ar atmosphere. As novel electrocatalysts for the hydrogen evolution reaction(HER), cc-WCNPs exhibit an onset potential of -0.14 V vs. reversible hydrogen electrode(RHE) and a Tafel slope of 64.6 mV/dec in a 0.5 mol/L H2SO4 solution. Additionally, these cc-WCNPs catalysts also show excellent electrocatalytic stability after 1000 cycles.

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LI Chao, FANG Mengxiang, XIAO Ping, SHI Zhenghai, CEN Jianmeng, YAN Qike, WANG Qinhui, LUO Zhongyang
Investigation of the Evolution Behavior of Light Tar During Bituminous Coal Pyrolysis in a Fluidized Bed Reactor
2016 Vol. 32 (6): 1019-1027 [Abstract] ( 1 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-016-6091-9

The evolution behavior of the light tar fraction of tar during large bituminous coal particle pyrolysis in a fluidized bed reactor at 500-900℃ was investigated to optimize the industrial process. The coal residence time was varied from 30 s to 150 s. The crude tar obtained was distilled and separated into the light fraction and the heavy fraction through an evaporator under conditions of 280℃ and 104 Pa. The light tar was subjected to GC-MS analysis, and the 300 main species in each spectrum were determined and analyzed. The experimental results showed that the evolution behavior of the light tar fraction and the heavy tar fraction presented spectacularly different variation trends with pyrolysis temperature and coal residence time. The molecular weight and number of rings per aromatic compound molecule contained in the light tar fraction increased with increasing pyrolysis temperature because of polymerization. It was also observed that the amount of methyl substituents decreased with an increasing number of rings per molecule of poly-aromatic ring compounds. The chain aliphatic compound evolution was suppressed and underwent heterocyclization with increasing temperature.

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YANG Wenhua, LÜ Wencai, XUE Xuyan, ZANG Qingjun, WANG Caizhuang
Studies on Optical Properties of Si220 Nanoclusters via Time-dependent Density Functional Theory Calculations
2016 Vol. 32 (6): 1028-1033 [Abstract] ( 8 ) [HTML 1KB] [PDF 0KB] ( 10 )   
doi: 10.1007/s40242-016-6085-7

The optical properties of bare and hydrogen passivated Si220 nanoclusters(NCs) in four typical motifs(i.e., bulk-like, onion-like, bucky-diamond and icosahedral motifs) were studied via time-dependent density functional theory(TD-DFT) calculations. The calculation results show that there is a significant blue shift in the optical absorption spectra when the Si NCs are passivated with hydrogen. A strong absorption peak in the visible light region appears for the hydrogenated bulk-like, onion-like and bucky-diamond Si NCs.

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ZHANG Peng, TAN Mingrui, SUI Ning, WANG Yinghui, TIAN Chunlin, ZHANG Hanzhuang
Charge Carrier Dynamics in PDPP-F/PCBM Heterojunction Solar Cells
2016 Vol. 32 (6): 1034-1037 [Abstract] ( 7 ) [HTML 1KB] [PDF 0KB] ( 12 )   
doi: 10.1007/s40242-016-6083-9

The morphology dependent of migration and recombination kinetics of charge carriers in the polymer solar cell based on poly {2,7'-9,9-dioctylfluorene-alt-5-diethylhexyl-3,6-bis(5-bromothiophen-2-yl)pyrrolo[3,4-c]-pyrrole-1,4-dione}(PDPP-F) was investigated with photo-induced charge carrier extraction by linearly increasing voltage technique. The recombination coefficient of charge carriers decreased and the mobility of charge carriers increased, after the mass ratio of[6,6]-phenyl-C61-butyric acid methyl ester(PCBM) increased from 3:2 to 2:1. Meanwhile, both of them were sensitive to the applied electric field and could be together responsible for the improvement of voltage performance of polymer solar cell.

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YU Yanmin, LI Hua, PIAO Lijin, CHEN Huiying, WANG Wenzhong, XIA Jianxin
Synthesis of Gd-N Codoped Porous TiO2 Photocatalyst and Its Enhanced Photocatalytic Activities
2016 Vol. 32 (6): 1038-1044 [Abstract] ( 72 ) [HTML 1KB] [PDF 0KB] ( 24 )   
doi: 10.1007/s40242-016-6074-x

Visible-light-active Gd-N codoped porous TiO2(Gd-N-TiO2) photocatalyst was fabricated by an evapora-tion-induced self-assembly route using surfactants as structure-directed agents. As-prepared samples were characterized by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy(TEM), X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller(BET) method, and ultraviolet-visible absorption spectroscopy. The results indicated that synergistic reaction occurred when codoping with Gd3+ and N, which enhanced the light absorption properties of TiO2. Irregular worm-like particles with wide interparticle spaces were clearly observed by TEM. The average particle size of Gd-N-TiO2 decreased to ca. 8 nm because co-doping inhibited the particles growth significantly. Thus, the specific surface area of Gd-N-TiO2(198.7 m2/g) was higher than that of Degussa P25 TiO2(50 m2/g). Gd-N-TiO2 exhibited a high photocatalytic activity toward methyl orange degradation under UV-Vis or visible-light irradiation. The Gd-N-TiO2 catalyst also presented a stable performance without losing activity after four successive photocatalytic experiments. The facile synthesis and excellent activity of Gd-N-TiO2 indicated its great potential as industrial catalysts for wastewater treatment.

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ZHANG Jihua, LI Jie, LIU Mingjie, ZHAO Yunfeng, WANG Shutao
Thermal Decomposition Kinetics and Mechanism of Low-temperature Hydrogenated Acrylonitrile Butadiene Rubber Composites with Sodium Methacrylate
2016 Vol. 32 (6): 1045-1051 [Abstract] ( 8 ) [HTML 1KB] [PDF 0KB] ( 21 )   
doi: 10.1007/s40242-016-6148-9

Thermal decomposition processes and mechanism of low-temperature grade hydrogenated acrylonitrile butadiene rubber(LTG-HNBR) composites with sodium methacrylate(NaMAA) were investigated by thermogravimetric analysis(TGA) and Fourier transform infrared spectroscopy(FTIR) coupling technology in this article. The results of TGA demonstrate that the addition of NaMAA can enhance the thermal decomposition temperature of the rubber. Moreover, it was found that the composites spent more activation energies to decompose than pure rubber by the calculations of multiply heating rate method. Time-resolved FTIR spectra show that NaMAA affects the initial decomposition of the composites. But in the following process, the composites maintained a similar behavior to the matrix. During the decomposition, PNaMAA nanostructures, in-situ generated by NaMAA, helped reduce the diffusion speed of decomposition products and thus improved the thermal stability of the composites. We believe that these findings can provide some guides to direct the applications of LTG-HNBR composites with unsaturated metal methacrylates.

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SHI Qing, WANG Gong, LÜ Chao, XIA Hong
Fabrication and Manipulation of Magnetic Composite Particles with Specific Shape and Size
2016 Vol. 32 (6): 1052-1056 [Abstract] ( 14 ) [HTML 1KB] [PDF 0KB] ( 20 )   
doi: 10.1007/s40242-016-6143-1

The fabrication of microscale polyethylene glycol diacrylate(PEGDA) hydrogel particles was demonstrated via magnetic property ultraviolet(UV) lithography techniques, polydimethylsiloxane(PDMS) soft stamp pre-paration techniques and micro-nano imprint technology in this paper. The results of compositional and morphological characterizations of magnetic microparticles show that the Fe3O4 nanoparticles with an average diameter of 100 nm are uniformly dispersed in hydrogel. Owing to the excellent magnetism of Fe3O4 nanoparticles, the fabricated hydrogel microparticles with different sizes and shapes were manipulated in water via applying an external magnetic fields. Three types of motions, translation, rotation and flip, were demonstrated with the manipulator. These microscale magnetic PEGDA hydrogel particles have a great application potential in manufacturing process, micro/nanomotors, and machines.

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HU Qiuxue, YAN Xinxin, DONG Chenjun, HU Wei
Chemical Modifications on Linen for Unsaturated Polyester Composites
2016 Vol. 32 (6): 1057-1062 [Abstract] ( 4 ) [HTML 1KB] [PDF 0KB] ( 10 )   
doi: 10.1007/s40242-016-6101-y

Linen was chemically modified by oleoyl chloride(OC) and stearoyl chloride(SC) to graft fatty moieties onto fiber via ester connections. Pyridine was used as solvent. The reaction was simplified by reacting the compounds in air at 60℃ for 6 h. Fourier transform infrared spectroscopy(FTIR) and thermal gravimetric analysis were conducted to characterize the treated fiber. The FTIR result confirms that the fatty portions have been successfully grafted onto the fiber after the chemical modification. The thermal stability of the SC-modified linen(SCL) was similar to that of the flax modified by oleoyl chloride(OCL). SCL and OCL demonstrated a temperature of 5% mass loss, which was above 200℃ and could meet the requirements of the processing conditions for most composites. Thereafter, the SCL-reinforced unsaturated polyester(UPE) composites were prepared and characterized. The composite presented a much better impact strength of 61.1 J/m and tensile modulus of 1.69 GPa than those of UPE with applicable thermal stability. SCL has been shown to be a promising choice as reinforcing material for composites.

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ZHONG Qiulin, ZOU Lu, WANG Yinghui, SUI Ning, LIU Qinghui, ZHANG Liquan, ZHANG Hanzhuang
Photo-induced Birefringence of Azo-dye Based on Three-dimensional Opal Photonic Crystals
2016 Vol. 32 (6): 1063-1068 [Abstract] ( 11 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-016-6042-5

A series of three-dimensional opal photonic crystals based on the polymer was synthesized and applied in the field of photo-induced birefringence. The data show that the photo-induced birefringence(PIB) of pure Sudan III film could be enhanced by increasing the thickness of azo films. When Sudan III was distributed on the three-dimensional opal photonic crystals, the photo-induced birefringence process could be modulated. In addition, the data also exhibit that the PIB processes with different pumping polarization directions are sensitive to the role of photonic crystals. The results could be beneficial to further understanding the photo-induced birefringence and utilizing the photonic crystals.

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