CHEMICAL RESEARCH IN CHINESE UNIVERSITIES
 
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2017 Vol.33 No.3
 Published: 01 June 2017

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Chemical Research in Chinese Universities Vol.33 No.3 February 2017
2017 Vol. 33 (3): 0-0 [Abstract] ( 10 ) [HTML 1KB] [PDF 2018KB] ( 14 )   
doi:

Articles
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LIU Yan, YU Dongdong, ZHU Wei, BAI Xiao, SHEN Qihui, LIU Xiaoyang, ZHOU Jianguang
Preparation of CdTe Nanocrystals Doped Fluorescent Silica Spheres by Sol-gel Method and Their Surface Modification via Thiol-ene Chemistry
2017 Vol. 33 (3): 327-332 [Abstract] ( 3 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-017-6496-0

A facile one-step sol-gel method was used to prepare CdTe nanocrystals(NCs) doped silica microspheres with luxuriant thiol group on their surface using 3-mercaptopropyl trimethoxysilane(MPTMS) as organosilane in the aqueous solution. As the ligand and organosilane, MPTMS ensured the doping efficiency of CdTe NCs by ligand exchange and a large thiol group exposed to the solution to activate the surface of silica microspheres. The remodeled sol-gel process was performed at a lower temperature, which protected the thiol groups from degradation. Meanwhile, the particle size and size distribution can be controlled by varying synthesis conditions, such as the stirring rate and the reaction temperature. This user-friendly method provides a platform for immobilization of chemical groups such as carboxyl for combination of bioactive and diagnostic molecules at the surface of CdTe NCs doped silica microspheres through thiol-ene chemistry for high-throughput microarrays.

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SONG Jiangfeng, WANG Jun, ZHOU Ruisha, CUI Xiaobing
A New Inorganic 2D Framework Based on Bi-bismuth-capping Keggin Polyoxometalate with Photodegradation and Selective Absorption of Organic Dyes
2017 Vol. 33 (3): 333-338 [Abstract] ( 4 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-017-6475-5

A new purely inorganic 2D framework, {PMo12O40Bi2(H2O)2}·4H2O(1), was synthesized under solvothermal condition and characterized by infrared(IR) spectroscopy, thermal gravimetric analysis, UV-Vis spectroscopy, powder X-ray diffraction and single-crystal X-ray diffraction. Structural analysis reveals that compound 1 consists of Keggin unit {PMo12O40} with two bismuth atoms capping two opposite pits, leading to the bi-bismuth-capping Keggin polyoxometalate. Compound 1 not only displays excellent photodegradation activity for methyl orange(MO), but also has a high absorption capacity for rhodamine B(RhB) and methylene blue(MB). Moreover, compound 1 is extremely stable and easily separated from the reaction system for reuse.

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LI Yanyan, YIN Lei, LI Yanhua, SUN Zhihui, ZHAO Xiaojun, GAO Mingyue, WANG Hongliang
Therapeutic Drug Monitoring of Vancomycin and Voriconazole by Liquid Chromatography-Tandem Mass Spectrometric Method
2017 Vol. 33 (3): 339-342 [Abstract] ( 14 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-017-7051-8

A reliable liquid chromatography-tandem mass spectrometric(LC-MS/MS) method was developed and validated for the simultaneous determination of vancomycin and voriconazole in human plasma. The analytes and internal standard 10-hydroxycarbazepine were separated at a flow rate of 0.9 mL/min using a Zorbax SB-C18 column (50 mm×4.6 mm, 2.7 μm). Positive ion electrospray ionization was used to detect vancomycin, voriconazole and intrenal standard(IS) 10-hydroxycarbazepine followed by multiple reaction monitoring(MRM) of the transition at m/z 725.5→144.2, 350.3→281.0 and 253.1→208.0, respectively. The total run time for both vancomycin and voriconazole samples was 5 min; 0.30 μg/mL was the lower limit of quantification. The precision of intraday and interday was no more than 12.4%. The method was successfully and resoundingly applied in therapeutic drug monitoring of 156 patients treated with vancomycin and voriconazole.

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YU Yang, WANG Xinghua, FEI Qiang, YU Yong, TIAN Sizhu, WANG Kun, JIANG Jia, SONG Daqian, YU Aimin, ZHANG Ziwei
Direct Determination of Migration Amount of Fluorescent Whitening Agents in Facial Mask
2017 Vol. 33 (3): 343-347 [Abstract] ( 21 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-017-6448-8

Facial mask is a kind of skin care cosmetics, in which fluorescent whitening agents(FWAs) were added to make face skin look whiter and brighter. In this work, pig skin was used instead of human skin to test the methods. Three methods, including pig skin migration fluorescent spectrophotometry(FS), fiber paper migration FS, and fiber paper migration visual colourimetry(VC), were developed for determining the migration amount of FWAs from facial mask to pig skin. In the methods, a self-assembly light source and fluorescence collecting unit was used. The unit can be easily moved and the measurement was very convenient. Some experimental conditions were optimized. The fiber paper migration VC can give semi-quantitative results and was the simplest one in the three methods because collection, separation and detection of the fluorescence were not needed. Both the pig skin migration FS and fiber paper migration FS can give quantitative results and compared with fiber paper migration FS, the pig skin migration FS could give more practical results by simulating the real way of using facial mask. The limits of detection for disodium 4,4'-bis[(4-anilino-6-hydroxyethylamion-1,3,5-triazin-2-yl)amion]stilbene-2,2'-disulphonate(VBL) obtained by pig skin migration FS and fiber paper migration FS were 0.03 and 0.05 mg/m2, respectively. 96 kinds of samples were analyzed and the migration amounts of FWAs in 21 kinds of samples were detectable. Correlations between migration amounts obtained by the three methods were very good. Experimental results indicate that the present methods can be applied to the determination of migration amount of FWAs in facial masks.

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LI Zhanchao, ZHANG Zhiquan, WU Lijie, WANG Jichang, LIU Zhenheng, ZHANG Zhongwei, ZHANG Hanqi, WANG Ziming
Preparation and Characterization of Two Wood Vinegars Obtained from Hull of Spina Date Seed and Shell of Peanut
2017 Vol. 33 (3): 348-353 [Abstract] ( 19 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-017-6416-3

Two new kinds of wood vinegars(WVs) from the hull of spina date seed(HSDS) and the shell of peanut(PS) were prepared. 32 Major components in the two kinds of WVs were identified and determined by gas chromatograph-mass spectrometery. The total phenolic content was determined and the antioxidant activity of the WV was measured. The total phenolic contents of PSWV and HSDSWV were 75.9 and 98.1 mg/L, respectively, when they were expressed as catechol equivalents. In 1,1-diphenyl-2-picrylhydrazyl assay, free radical scavenging activity of HSDSWV was also superior than that of PSWV. In addition, the antioxidant activities of the two kind of WVs exhibited a good positive correlation with total phenolic content, and the linear correlation coefficients ranged from 0.9594 to 0.9970. The two kind of WVs could be used in the fields of food and medicine due to their powerful antioxidant activities.

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Muhammad ASGHAR, Mohammad YAQOOB, Abdul NABI
Chemiluminescent Determination of Cyromazine in Milk Samples Using Copper (III) Chelate-Triton X-100 by Flow Injection Analysis
2017 Vol. 33 (3): 354-359 [Abstract] ( 35 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-017-6402-9

Cyromazine(CYR) was determined in milk samples using copper(III) chelate-Triton X-100 chemilumi-nescence(CL) system associated with flow-injection(FI) in KOH medium. The relative CL intensity for CYR concentration was linear over the range of 5×10-4-10 μg/mL(R2=0.9990, n=11) with injection rate of 160 h-1 and the relative standard deviation(RSD, n=4) of 1.2%-2.6%. The limit of detection(LOD) for signal-to-noise ratio of 3 was 1.5×10-4 μg/mL. The influences of key chemical and physical parameters, some major fresh water ions at their maximum admissible concentrations and a number of pesticides were examined as potential interferences. The concentrations of CYR in spiked milk samples were successfully determined by the proposed method and the results were in good agreement with that of the previously reported HPLC method, having recovery range of (92%±4%)-(106%±2%). The possible CL reaction mechanism for copper(III) chelate-Triton X-100-CYR was also briefly discussed.

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KE Yuqiu, GUO Wei, JIN Lanlan, QIAO Lei, YANG Huan, HU Shenghong
Direct Quantitative Determination of Rare Earth Elements in REE-rich Mineral Powders by LA-ICP-MS
2017 Vol. 33 (3): 360-364 [Abstract] ( 28 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-017-6399-0

For direct quantitative determination of rare earth elements(REE) in REE-rich minerals, a most acceptable reference material NIST 610 might be an alternative external calibration standard due to the lack of matrix-matched reference materials. Here, we aimed to develop an analytical method for direct quantitative determination of REE concentrations in REE-rich minerals via laser ablation-inductively coupled plasma-mass spectrometry(LA-ICP-MS). The results show that the REE concentrations measured via LA-ICP-MS using NIST 610 as an external standard are in good agreement with reference values with relative percentage difference(Dr) mainly less than 15%. Overall, these results demonstrate that our proposed analytical method is robust and accurate for direct quantitative determination of REE concentrations in REE-rich minerals.

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ZHANG Lan, DENG Xinshan, WU Jiaofeng, MENG Guangpeng, LIU Congchong, CHEN Guzhou, ZHAO Qingchun, HU Chun
Design, Synthesis and Biological Activities of N-(Furan-2-ylmethyl)-1H-indole-3-carboxamide Derivatives as Epidemal Growth Factor Receptor Inhibitors and Anticancer Agents
2017 Vol. 33 (3): 365-372 [Abstract] ( 16 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-017-7041-x

A series of N-(furan-2-ylmethyl)-1H-indole-3-carboxamide derivatives(6a-6p) was designed and synthesized for developing novel indole scaffolds as anticancer agents targeting the epidemal growth factor receptor (EGFR), and the cytotoxic activities of the target compounds were evaluated against three EGFR high-expressed cancer cell lines[human lung adenocarcinoma cell line(A549), Henrietta Lacks strain of cancer cell line(HeLa) and human colorectal cancer cell line(SW480)], one EGFR low-expressed cell line(human liver cancer cell line, HepG2) and one human liver normal cell line(HL7702) using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) assay. Some target compounds exhibited potent anticancer activities against A549, HeLa, SW480 and weak activities on HepG2, which signifies that the target compounds are likely to be EGFR inhibitors as expected. And they showed weak cytotoxic effects on HL7702, which implies the target compounds are probably to be of low toxicity against normal cells. Among them, the target compound 1-ethyl-N-(furan-2-ylmethyl)-5-{2-{[2-(2-methoxy-phenoxy)ethyl]amino}-2-oxoethoxy}-2-methyl-1H-indole-3-carboxamide(6p) with 2-{[2-(2-methoxyphenoxy)ethyl]-amino}-2-oxoethoxy group at the C5 position of the N-(furan-2-ylmethyl)-1H-indole-3-carboxamide scaffold exhibited the most potent anticancer activity. Also the binding interaction of the target compound 6p with EGFR was explored by molecular docking. Conclusively, the novel indole scaffold may be beneficial to investigate new anticancer agents for targeting the EGFR.

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Ahmed A. EL-GOKHA, Nader M. BOSHTA, Mona K. ABO HUSSEIN, Ibrahim EL-T. EL SAYED
Synthesis and Structure-Activity Relationships of Novel Neocryptolepine Derivatives
2017 Vol. 33 (3): 373-377 [Abstract] ( 21 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-017-6502-6

Herein we reported the synthesis of a novel series of neocryptolepine(5-methyl-5H-indolo[2,3-b]quinoline) derivatives containing different substituents at C11 using methyl 1H-indole-3-carboxylate and N-methylaniline as starting material. The target 21 compounds were evaluated for their antibacterial activity in vitro against gram-positive bacteria(B. subtilis and S. aureus) and gram-negative bacteria(E. coli and vS. typhi). Almost all the tested compounds showed moderate to high activities against the four bacterial strains at the minimum inhibitory concentrations(MICs) of 1-10 μg/mL. The obtained results suggest that part of the novel synthetic neocryptolepine derivatives exhibit significant antibacterial effect against all the tested organisms.

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LIANG Guangping, CHUNG Tseyu, GUO Jinhua, ZHANG Rongrong, XÜ Wei, TZEN Jason T. C., JIANG Renwang
Novel Cinobufagin Oxime Ether Derivatives as Potential Na+/K+-ATPase Inhibitors: Synthesis, Biological Screening and Molecular Docking
2017 Vol. 33 (3): 378-383 [Abstract] ( 29 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-017-6487-1

Some cinobufagin oxime ether derivatives as potential Na+/K+-ATPase inhibitors were synthesized by following the side chain of istaroxime. These compounds inhibit Na+/K+-ATPase in a dose-dependent manner. Compound 3c with an oxyethylamine side chain that is the same as that of istaroxime showed the most potent inhibition, which was stronger than compound 3a with only hydroxyoxime moiety at C3 and compound 3b with a methylated hydroxyoxime moiety. Molecular docking was used to explore the binding modes of the target compounds with Na+/K+-ATPase, which suggested that the longer ethyl amine group at C3 oxime moiety of compound 3c could make stronger interaction with Na+/K+-ATPase via intermolecular charge-charge and H-bond interaction as compared with other derivatives.

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ZHANG Xiaopeng, LI Zhengwei, WANG Ping, FAN Xuesen, ZHANG Guisheng
Selenium-catalyzed Oxidative Carbonylation of Benzylamines to 1, 3-Dibenzylureas
2017 Vol. 33 (3): 384-387 [Abstract] ( 38 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-017-6427-0

A facile, efficient and cost-effective approach to 1,3-dibenzylurea was reported. With cheap and recyclable nonmetal selenium as catalyst, carbon monoxide instead of phosgene derivatives as carbonylation agent and oxygen as oxidant, the selenium-catalyzed oxidative carbonylation reaction of benzylamines can proceed efficiently in one-pot manner in the presence of triethylamine to afford the desired 1,3-dibenzylureas mostly in moderate to excellent yields. Selenium catalyst can be easily recovered due to its phase-transfer catalytic function and recycled.

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PAN Ying, WANG Ke, LIU Yichen, QIN Rui, CAO Lu, WANG Jia, ZHOU Guanghong, ZHANG Aichen
In vivo Inhibitory Effect of Lentivirus-mediated RNA Interference Targeting RhoC on Growth of SKOV3 Cells
2017 Vol. 33 (3): 388-391 [Abstract] ( 7 ) [HTML 1KB] [PDF 0KB] ( 2 )   
doi: 10.1007/s40242-017-7090-1

To investigate the inhibitory effect of lentivirus-mendiated RNA interference targeting RhoC on the growth of SKOV3 cells(ovarian cancer SKOV3 cells) in vivo, the vector expressing RNA interference targeting RhoC gene(LV-shRhoC) was constructed and the virus particles were packaged. The infection effiency of SKOV3 cells by the virus was estimated by green fluorescent protein expression on a fluorescence microscope and the expression of RhoC gene in the SKOV3 cells was detected by reverse transcription real time polymerase chain reaction(PCR). Furthermore, human ovarian cancer SKOV3 cells, empty vector infected SKOV3 cells and interfered-vector infected SKOV3 cells were respectively seeded into nude mice, and the shape, mass, volume and histophathological changes of the transplanted tumors were observed 20 d later the mice were sacrified. The results show that lentivirus packa-ging particles can effectively infect SKOV3 cells and the lentivirus-mediated RNA interference can significantly inhibit the expression of RhoC gene in SKOV3 cells, the mass and volume of the transplanted tumor in the mice of the specific-control group(Lv-shRhoC) are all lower than the corresponding ones in the mice of negative-and blank-control groups(Lv-NC and SKOV3). Moreover, the histopathlosical secion investigation shows that the nuclear Karyotype and histopathologic mitotic figure of SKOV3 cells in mice of the specific-control group are clearly lower than those in the mice of the negative-control group.Thus it is concluded that silencing RhoC gene by means of lentivirus-mediated RNA interference targeting RhoC can obviously inhibit the growth of ovarian cancer cells(SKOV3) in vivo, which is a new strategy for the gene therapy of ovarian cancers.

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PAN Dong, WANG Lincong, LIU Meiyi, JIN Shi, WANG Liyan, YU Xianghui, ZHA Xiao, WU Yuqing
Effects of Site-directed Mutagenesis of L469 in Helix-5 of Human Papillomavirus 16 L1 on Pentamer Formation
2017 Vol. 33 (3): 392-399 [Abstract] ( 25 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-017-6357-x

Located at the carboxyl terminal of the human papillomavirus major capsid protein L1, helix-5(h5) is crucial to L1 folding and pentamer formation. Site-directed mutagenesis of the leucine residue on site 469 into lysine, alanine, serine and glycine was performed to explore the effect of the resultant mutations on L1 pentamer formation. The soluble yields of the L1 pentamers of the L469A and L469K mutants were nearly two fold higher than that of the wild type. Molecular dynamics simulation was then performed to reveal the intrinsic mechanisms involved in the improvement of L1 pentamer yield. Accordingly, the secondary structures of h5, β-G2, β-B1, β-C, β-D, and β-F were altered. The altered structures improved the hydrophobic interaction between h5 and β-core "jelly" and the stability of h5. The hydrophobic surface area of residue 469 was reduced by 50% relative to that of the wild type. The C-O group of residue 469 and C-N group of L470 were both exposed to the solvent in the L469A mutant. These modifications may account for the increased solubility and stability and the promotion of pentamer formation induced by the point mutation. Therefore, the changes in the hydrophobic properties of h5 and the core structure determined the pentamer formation and solubility. This study may assist the development of a cost-effective platform for the production of prophylactic virus-like particle vaccines.

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ZHONG Qiulin, CHEN Ying, WANG Yinghui, CHI Xiaochun, WANG Yue, NI Moucui, ZHANG Hanzhuang
Dynamic Mechanism of Relaxation Paths Occurring in TPA-DCPP: Roles of Solvent and Temperature
2017 Vol. 33 (3): 400-405 [Abstract] ( 14 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-017-6506-2

The relaxation paths for triphenylamine(TPA)-2,3-dicyanopyrazino phenanthrene(DCPP), which has a pull-push structure, were investigated via steady-state, time-resolved spectroscopy involving transient absorption and time-correlated single photon counting. By changing the solvent polarity we found that an intramolecular charge transfer(ICT) state acting as a "bright" state was responsible for the fluorescence character of TPA-DCPP. Meanwhile, a "dark" state gradually appeared and competed with the ICT state. This was likely to be responsible for the polarity-dependent evolution of fluorescence intensity and fluorescence lifetime. The temperature-dependent fluorescence character of the TPA-DCPP in toluene exhibited ICT processes at high temperatures prior to the relaxation path from the initial excited state to the ground state. Our results provide useful insight into the optoelectronic properties of these kinds of molecules.

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LÜ Cunqin, LIU Jianhong, JIN Chun, GUO Yong, WANG Guichang
A DFT+U Investigation on Methylamine Decomposition Catalyzed by Pt4 Cluster Supported on Oxygen Defective Rutile (110) TiO2
2017 Vol. 33 (3): 406-414 [Abstract] ( 15 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-017-6489-z

The adsorption and decomposition mechanisms of methylamine catalyzed by Pt4 cluster supported on rutile(110) titania[namely, Pt4/TiO2-R(110)] were investigated via density functional theory slab calculations with Hubbard corrections(DFT+U). The adsorption energies under the most stable configuration of the possible species and the energy barriers of the possible elementary reactions involved in methylamine decomposition were obtained. Through systematic calculations for the reaction mechanism of methylamine decomposition on the Pt4/TiO2-R(110), the most possible decomposition path is CH3NH2→CH2NH2+H→CH2NH+2H→CHNH+3H→HCN+4H→CN+5H, which is similar to that of methylamine dissociation catalyzed by Pt(100) surface.

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ZHAO Yongsheng, LI Qin, REN Hejun, ZHOU Rui
Activation of Persulfate by Magnetic MnFe2O4-bentonite for Catalytic Degradation of 2, 4-Dichlorophenol in Aqueous Solutions
2017 Vol. 33 (3): 415-421 [Abstract] ( 20 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-017-6485-3

Magnetic MnFe2O4-bentonite was synthesized by chemical co-precipitation method(CCM) and applied as catalyst in heterogeneous activation of persulfate(PS) to oxidize a target pollutant, 2,4-dichlorophenol(2,4-DCP), in aqueous solutions. The surface morphology and structure of MnFe2O4-bentonite were characterized by X-ray diffrac-tion(XRD), scanning electron microscope(SEM), energy dispersive X-ray(EDX) and X-ray photoelectron spectros-copy(XPS) analyses.The catalytic activity of MnFe2O4-bentonite for 2,4-DCP degradation was evaluated considering the effects of various process parameters, such as mass ratio of MnFe2O4 to bentonite, concentration of catalyst, PS concentration, and pH. The MnFe2O4-bentonite hybrid exhibited higher catalytic activity than pure MnFe2O4. Treatment with 5 g/L MnFe2O4-bentonite at 30℃ for 240 min oxidized 92% of 100 mg/L 2,4-DCP(70.2% mineralization), whereas treatment with pure MnFe2O4 under the same condition oxidized only 70% of the pollutant. This result indicate the enhanced performance of the activated PS. Moreover, MnFe2O4-bentonite exhibits stable performance with minimal loss in activity after five successive runs. Thus, MnFe2O4-bentonite could be a promising catalyst in oxidative degradation of 2,4-DCP.

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XIAO Lu, CHU Wei, SUN Wenjing, XUE Ying, JIANG Chengfa
Enhancement of Hydrogen Sorption on Metal (Ni, Rh, Pd) Functionalized Carbon Nanotubes: a DFT Study
2017 Vol. 33 (3): 422-429 [Abstract] ( 13 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-017-6436-z

Hydrogen interacted with pristine single-walled carbon nanotubes(SWNTs) and single/dimer metal doped ones(M-CNTs) was investigated via density functional theory(DFT) simulations. The most stable configurations of Ni, Rh, Pd on SWNTs were identified. The interaction of H2 molecules with pristine SWNTs and M-CNTs was investigated. The results show that H2 molecules can be adsorbed on the pristine SWNTs via a weak physical interaction, which is much weaker than those of H2 molecules with M-CNTs by chemisorption. Each Ni, Rh and Pd doped SWNTs can respectively chemisorb three, two, or one H2 molecules and the H-H bond of H2 molecule is elongated. Furthermore, the H2 molecule could be dissociated owing to the presence of the Ni-Ni bond for Ni dimer doped SWNT, forming new Ni-H bonds. While such a dissociation could not be observed on Rh2/Pd2-CNT samples. Density of state(DOS) results show that the s orbital of hydrogen can hybridize with the d orbital of metal atom, resulting in the stronger inteaction between H2 and M-CNTs, impying that the hydrogen storage capacity could be enhanced in the presence of M-CNTs. The comparison of the interaction mechanism among different metals doped CNTs can screen out the most effective hydrogen-adsorption materials and the design of the related materials by computational approaches.

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DU Pengfei, CHEN Guoxu, SONG Shiyuan, ZHU Dachuan, WU Jiang, CHEN Peng, CHEN Hanlin
Preparation and Tribological Properties of Cu-doped Muscovite Composite Particles as Lubricant Additive
2017 Vol. 33 (3): 430-435 [Abstract] ( 16 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-017-6418-1

Cu-doped muscovite(Mu) composite particles, abbreviated as Mu/Cu, were prepared via liquid phase reduction method. The morphologies, phase composition and elementary distribution of the as-prepared Mu/Cu and raw muscovite particles were characterized by means of scanning electron microscope(SEM), X-ray diffraction(XRD) and energy dispersive spectrometry(EDS). The tirbological properties of Mu/Cu and Mu as lubricant additives in lithium grease were evaluated on a block-ring tribomachine. The roughness, 2D and 3D morphologies and elementary distribution of block worn surface were analyzed to explore the tribogical mechanism. The results show that muscovite are evenly coated by the cubic Cu nanoparticles in composite particles. Both Mu/Cu and Mu can effectively improve the tirbological properties of lithium grease and Mu/Cu exhibits better tribological performance than Mu. The friction coefficient of Mu/Cu is decreased by 69.2% as compared to that of lithium grease. The layer structure of muscovite is synergistic with Cu nanoparticles in contribution to the formation of lubricant film mainly consisting of O, Si, Fe, Cu as well as Al elements on the block worn surface thereby further reducing the friction and wear.

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CUI Shu, LI Xuesong, LI Yanjuan, ZHAO Haixin, WANG Yuanyuan, LI Nan, LI Xiaotian, LI Guodong
Synthesis of CdS/m-TiO2 Mesoporous Spheres and Their Application in Photocatalytic Degradation of Rhodamine B Under Visible Light
2017 Vol. 33 (3): 436-441 [Abstract] ( 8 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-017-6377-6

CdS/m-TiO2 heteroarchitecture with CdS nanocrystals loaded on mesoporous TiO2(m-TiO2) spheres was successfully synthesized via sol-gel method followed by solvothermal treatment. The material with uniform diameter of ca. 750 nm possesses regular mesoporous structure and large specific surface area of 100.5 m2/g. When used to photodegradate Rhodamine B(RB) under visible light, the CdS/m-TiO2 heteroarchitecture exhibits improved photocatalytic performance in comparison with pure m-TiO2 or CdS. The excellent photocatalytic activity is closely related to the facilitated separation of electron-hole pairs derived from the CdS/m-TiO2 heterojunction and mesoporous structure with high specific surface area and adequately exposed active sites.

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WANG Licheng, BU Tiantong, WANG Zhenlü
Preparation of Cu-MgO Catalysts via Urea-nitrate Combustion Method and Their Catalytic Performance in Vapor Phase Hydrogenation of Furfural
2017 Vol. 33 (3): 442-446 [Abstract] ( 42 ) [HTML 1KB] [PDF 0KB] ( 16 )   
doi: 10.1007/s40242-017-6315-7

A series of Cu-MgO catalysts was prepared via a urea-nitrate combustion method, and their catalytic per-formance was examined in the vapor phase hydrogenation of furfural. Characterization results showed that the amount of urea had important effects on the surface area, Cu dispersion and crystallite size of the catalysts. The Cu-MgO catalyst with a Cu loading of 12.1%(mass fraction) showed higher furfural conversion than the catalyst prepared by coprecipitation. The high activity was attributed to the higher dispersion of Cu on the catalyst surface. These results suggest that the combustion method is an efficient and simple route for the preparation of high activity Cu-MgO catalysts for furfural hydrogenation.

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WANG Juan, SUN Runguang, HAO Changchun, LI Tuo, TIAN Yuan, ZHANG Lei
Influence of Metal Cations and Cholesterol on Lipid-amphotericin Membrane
2017 Vol. 33 (3): 447-453 [Abstract] ( 24 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-017-6303-y

Amphotericin B(AmB) has been widely used in antifungal therapy. AmB molecules combine with cholesterol to form pores that can be toxic to human cells, thus greatly limiting its clinical application. The interaction between AmB and the cell membrane may be influenced by potassium, sodium and calcium ions. In this study, the bilayer in large unilamellar lipid-drug liposomes with or without cholesterol was employed as a model membrane. N-(7-Nitrobenz-2-oxa-1,3-diazol-4-yl)-1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine(NBD-PE) and 1-palmi-toyl-2-[6-(7-nitrobenz-2-oxa-1,3-diazol-4-yl)aminodoclecanoyl]-sn-glysero-3-phosphocholine(6-NBD-PC) are two kinds of fluorescent lipid probes, and the NBD group is attached to the polar lipid headgroup in the former, but to the sn-2 fatty acyl chain in the latter. The effect of these metal cations on the lipid-drug membrane was monitored by red edge excitation shift(REES), fluorescence polarization, and the fluorescence lifetime of lipid probes in hydrophilic and hydrophobic areas of the membrane. These ions have different effects on the lipid-AmB membrane. Cholesterol can strengthen the packing ability of the membrane, which is influenced differently by potassium, sodium and calcium ions. Moreover, the influence of these ions on the membrane may be relative to the method of ion transportation through the membrane. This study is significant to understand the reduction of AmB's cellular toxicity.

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LI Xiang, WANG Kun, XIE Mengya, WU Zhu, XIE Leidong
Thermodynamic and Phase Diagram Modeling of CsF-MF4(M=U, Th) Systems
2017 Vol. 33 (3): 454-459 [Abstract] ( 22 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-017-6282-z

Phase diagrams for the CsF-UF4 and CsF-ThF4 systems were modeled in the present work through com-putational thermodynamics. The associate solution model with various complex species(CsMF5, Cs2MF6 and Cs3MF7; M=Th, U) was used to thermodynamically describe the binary molten salts. A total of ten intermediate phases were treated as stoichiometric compounds with their Gibbs energies modeled according to the Neumann-Kopp rule. All these model parameters were optimized by the least squares procedure until good coincidence was achieved between the calculated results and most of the experimental data. The derived thermodynamic parameters will be merged into the multicomponent CsF-LiF-BeF2-ThF4-UF4 database for analyzing physicochemical behavior of CsF in the fuel salt of the molten salt breeder reactor.

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CUI Ruizhi, YANG Lei, WANG Wei, SANG Shihua
Measurements and Calculations of Solid-liquid Equilibria in Quaternary System Li2SO4-Na2SO4-K2SO4-H2O at 288 K
2017 Vol. 33 (3): 460-465 [Abstract] ( 17 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-017-6275-y

The isothermal dissolution equilibrium method has been used to investigate the solid and liquid equilibria of quaternary system Li2SO4-Na2SO4-K2SO4-H2O at 288 K. The phase diagram and water diagram were plotted according to the experiment results. It was found that Li2SO4-Na2SO4-K2SO4-H2O quaternary system contains four double salts at 288 K. There are six invariant points, twelve univariant curves and seven areas of crystallization:Li2SO4·H2O, Na2SO4·10H2O, K2SO4, Li2SO4·3Na2SO4·12H2O, Li2SO4·K2SO4, Na2SO4·3K2SO4, 2Li2SO4·Na2SO4· K2SO4. Using the equilibrium solubility data of the quaternary system at 288 K, the solubility product(lnKsp) of solid phase 2Li2SO4·Na2SO4·K2SO4, which is not reported was acquired. Based on the chemical model of Pitzer's electrolyte solution theory, the solubilities for the quaternary system Li2SO4-Na2SO4-K2SO4-H2O at 288 K were calculated with corresponding parameters. Compared the results of experimental measurement with those of calculation, it was shown that the calculated values had a good agreement with the experimental ones.

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ZHANG Chunxia, XU Xu, ZHANG Panpan, DANG Yang, KANG Bonan
Polymer Solar Cells with Improved Power Conversion Efficiency Using Solvent Mixtures
2017 Vol. 33 (3): 466-470 [Abstract] ( 26 ) [HTML 1KB] [PDF 0KB] ( 2 )   
doi: 10.1007/s40242-017-6266-z

In this paper, the effects of solvent mixtures on the morphology, charge transport, and light trapping of poly[N-900-hepta-decanyl-2,7-carbazole-alt-5,5-(40,70-di-2-thienyl-20,10,30-benzothiadiazole)](PCDTBT) and[6,6]-phenyl C71-butyric acid methyl ester(PC71BM) based solar cells were investigated. As a good solvent for PCDTBT, o-dichlorobenzene(ODCB) was selected to mix with chloroform(CF), chlorobenzene(CB), and 1,2,4-Trichloroben-zene(TCB) for optimizing the morphology of the PCDTBT:PC71BM active layer. It can be found that the device performance of polymer solar cells(PSCs) has been greatly improved when using a optimal blend ratio. Especially, the PSCs fabricated via ODCB(90%)/CF(10%, volume fraction) mixture exhibit a remarkable enhancement of photon-to-current efficiency(PCE) from 5.16% to 7.47%. The enhanced performance of the PSCs can be attributed to the higher absorption, the lower resistance, and the optimized surface morphology of the active layers modified by the solvent mixtures.

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SEYFI Sara, AZADMEHR Amir Reza, MAGHSOUDI Abbas
Comparative and Competitive Adsorption of Cu (II) and Cd (II) Using Scoria: Equilibrium, Kinetic and Thermodynamic Studies
2017 Vol. 33 (3): 471-478 [Abstract] ( 5 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-017-6225-8

Heavy metals, such as Cu(II) and Cd(II) are among the hazardous pollutants that lead to severe ecological problems and have a toxic effect on living organisms. This study was carried out on adsorption of Cu(II) and Cd(II) from single-and multi-component aqueous solutions with Iranian scoria. Two-and three-parameter isotherm models, such as Langmuir, Freundlich, Temkin, Dubinin-Radushkevich, Khan and Toth have been studied for single and binary adsorption of Cu(II) and Cd(II) onto scoria. The best result was attained from Langmuir model for Cu(II) and Cd(II) ions in single and binary solution. Therefore, homogenous adsorption is dominated, which was emphasized by three-parameter isotherm models. Based on the value of the free energy of adsorption for Cu(II) and Cd(II), the interaction between these ions and scoria is a physical adsorption. In order to investigate competitive adsorption behavior, modified and extended Langmuir and Freundlich models have been studied, which indicated that adsorption of Cu(II) and Cd(II) on scoria has synergistic behavior. Extended Freundlich model and modified Langmuir model described Cu(II) and Cd(II) adsorption onto scoria, respectively.

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SHAN Liang, WANG Li, FAN Yong, SHEN Lanlan, WANG Shengyan, XU Jianing
Hyper-crosslinked Porous Polymer Based on Bulk Rigid Monomer for Gas and Dye Absorptions
2017 Vol. 33 (3): 479-483 [Abstract] ( 19 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-017-6467-5

Using the rigid 3,3-bis(4-hydroxyphenyl)-2-(4-tritylphenyl)isoindolin-1-one with polar functional groups as a building block and formaldehyde dimethyl acetal(FDA) as crossinglinker, a new hyper-crosslinked polymer (HCP) was synthesized via Friedel-Crafts alkylation reaction promoted by anhydrous FeCl3. The synthesized HCP is insoluble in boiled water and common organic solvents. Moreover, it shows a good CO2 capture capacity even if its surface area is not very high, and the absolute CO2 uptake capacity of it is 3.05 mmol/g. This can be attributed to the introduction of polar hydroxyl and lactam groups into the skeleton of the polymer, which provides effective adsorption sites for CO2. In addition, the synthesized HCP also exhibits good adsorption capacity for organic dyes in water, especially for crystal violet.

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XU Jiaqi, YI Xiaoqing, ZHAO Dan, YUAN Gongdao, ZHUO Renxi, LI Feng
A Three-drug co-Delivery System Based on Reduction-sensitive Pol-ymeric Prodrug to Effectively Reverse Multi-drug Resistance
2017 Vol. 33 (3): 484-491 [Abstract] ( 23 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-017-6450-1

In the present study, we prepared a multi-drug delivery system based on reduction-sensitive paclitaxel (PTX) polymeric prodrug(PEG-b-PMPMC-g-PTX, PMP) polymersomes to co-deliver PTX, doxorubicin hydrochlo-ride(DOX·HCl) and the P-glycoprotein(P-gp) inhibitor Tariquidar(TQR) to effectively reverse drug resistance by inhibiting the expression of P-gp and improving the accumulation of the encapsulated anticancer drugs. The PTX was linked to the backbone by reduction-sensitive disulphide, making the polymersomes prone to collapse in the reductive environment and to release the drugs. Transmission electron microscope(TEM) was used to confirm the morphology of polymeric assemblies. Moreover, the rupture process of polymersomes was verified by dynamic light scattering (DLS). The results of confocal laser scanning microscopy(CLSM) and flow cytometry indicate that the PMP/DOX·HCl/TQR three-drug-loaded polymersomes show the strongest fluorescence intensity for DOX·HCl compared with PMP/DOX·HCl polymersomes and free DOX·HCl in drug-resistant MCF-7/ADR cells. More importantly, the PMP/DOX·HCl/TQR multi-drug co-delivery system shows a greater growth-inhibitory effect on tumour cells than the other two samples, including PMP/DOX·HCl nanoparticles without the TQR component and free DOX·HCl, when co-incubated with either nonresistant HeLa cells or drug-resistant MCF-7/ADR cells. This growth-inhibitory effect was especially evident in drug-resistant cells. These results imply that the co-delivery of PTX, DOX·HCl and TQR based on reduction-sensitive polymeric prodrug may be promising for overcoming multi-drug resistance in tumour treatments.

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WANG Aijuan, DUAN Yuzhe, GU Xiaoyu, ZHANG Sheng, ZANG Wenhui
Surface Modification of Polyamide66 Fabric by Grafting with Vinyltrimethoxysilane
2017 Vol. 33 (3): 492-498 [Abstract] ( 20 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-017-6388-3

Melt-dripping is always a big chanllenge in flame retardant finishing of synthetic fabrics. In this work, vinyltrimethoxysilane(VTMS) was introduced onto the polyamide66(PA66) surface by microwave grafting to improve the fire performance. The chemical structure of the grafted fabric was characterized by attenuated total reflection Fourier transformation infrared spectroscopy(ATR-FTIR) and X-ray photoelectron spectroscopy(XPS). The thermal stability analysis and flammability evaluation of the grafted samples by thermogravimetric analysis(TGA), cone calorimetry, vertical burning tests and limiting oxygen index(LOI) demonstrate that the presence of grafting chains significantly reduces the dripping tendency and decreases the heat release rate of polyamide66(PA66) fabric. The surface morphology observed by scanning electron microscope(SEM) indicates that VTMS can not only promote the formation of protective layers, which prevent the substrate from further thermal degradation, but also promote the char formation of PA66 substrate during combustion.

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DONG Shujun, WANG Lin, LI Qiushi, CHEN Xuesi, LIU Shujie, ZHOU Yanmin
Poly (L-lactide)-grafted Bioglass/Poly (lactide-co-glycolide) Scaffolds with Supercritical CO2 Foaming Reprocessing for Bone Tissue Engineering
2017 Vol. 33 (3): 499-506 [Abstract] ( 7 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-017-6341-5

The bioglass particles/poly(lactide-co-glycolide)(BG/PLGA) scaffold has been extensively explored for biomedical applications due to its excellent advantages of mechanical property and controllable degradation rate. In our previous studies, the BG nanoparticle surface-grafted with poly(L-lactide)(PLLA) could substantially improve the phase compatibility between the polymer matrix and the inorganic phase and the biocompatibility of the scaffolds. However, using the traditional preparation methods to prepare the composite scaffold can barely achieve a high porosity and porous connectivity. In this work, the PLLA-grafted bioglass/PLGA(g-BG/PLGA) scaffolds were prepared by supercritical carbon dioxide foaming(Sc-CO2) with before or after particulate leaching(PL) method(Sc-CO2-PL or PL-Sc-CO2 method, PL/Sc-CO2 methods) and their applications in bone replacement and tissue engineering were investigated. The porosities of the g-BG/PLGA scaffolds prepared by the PL/Sc-CO2 methods were higher than 90%, and their mechanical properties had similar values with human cancellous bone. The proliferations of osteoblasts on the scaffolds were dependent on different preparation methods. The PL/Sc-CO2 methods significantly increased the proliferations of the cells. Computed tomography(CT) three-dimensional(3D) reconstruction tomographies of the implantation study for repairing calvarium defects of rabbits demonstrated that the calvarium defects were almost completely filled by the osteotylus in PL/Sc-CO2 method group at 12 week post-surgery, while there was little callus formation in PL method group and untreated control group. These results indicate that the g-BG/PLGA scaffolds prepared by the PL/Sc-CO2 methods exhibit rapid mineralization and osteoconductivity and are the optimal composites for bone repair.

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GUO Zhuo, LUO Xianke, LI Yahui, LI Dongdi, ZHAO Qinai, LI Mengmeng, MA Chi, ZHAO Yanting
Simultaneous Electrochemical Determination of Ascorbic Acid, Dopamine and Uric Acid Based on Reduced Graphene Oxide-Ag/PANI Modified Glassy Carbon Electrode
2017 Vol. 33 (3): 507-512 [Abstract] ( 7 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-017-6473-7

An electrochemical method for simultaneous determination of ascorbic acid(AA), dopamine(DA) and uric acid(UA) was developed based on RGO-Ag/PANI modified glassy carbon electrode(RGO-Ag/PANI/GCE, RGO=reduced graphene oxide, PANI=polyaniline). Owing to the synergetic effect among RGO, Ag and PANI, the RGO-Ag/PANI based sensor not only improved the electrochemically catalytic oxidation of AA, DA and UA, but also resolved the overlapping anodic peaks. Under the optimized conditions, the calibration curves were obtained in the concentration ranges of 50-1000, 5-200 and 20-350 μmol/L, and the detection limits(S/N=3) of 0.5, 0.2 and 0.2 μmol/L were obtained for AA, DA, and UA, respectively, in neutral phosphate buffer solutions(PBS). The RGO-Ag/PANI/GCE sensor was successfully applied to the determination of AA, DA, and UA in bovine serum samples and showed high selectivity, sensitivity, and reproducibility.

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