CHEMICAL RESEARCH IN CHINESE UNIVERSITIES
 
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2016 Vol.32 No.2
 Published: 01 April 2016

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Chemical Research in Chinese Universities Vol.32 No.2 December 2016
2016 Vol. 32 (2): 0-0 [Abstract] ( 50 ) [HTML 1KB] [PDF 1033KB] ( 131 )   
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Articles
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WANG Yang, LIU Xiaowei, ZHANG Haifeng, ZHOU Zhiping
Fabrication of Superhydrophobic Surface with Different Metal Films on Aluminum Alloy
2016 Vol. 32 (2): 155-158 [Abstract] ( 53 ) [HTML 1KB] [PDF 0KB] ( 41 )   
doi: 10.1007/s40242-016-5326-0

A simple technique was developed for the fabrication of a superhydrophobic surface on the aluminum alloy sheets. Different hierarchical structures(Ag, Co, Ni and Zn) were formed on the aluminum surface by the galvanic replacement reactions. After the chemical modification of them with fluorination, the wettability of the surfaces was changed from superhydrophilicity to superhydrophobicity. Scanning electron microscopy(SEM), energy dispersive spectrometry(EDS) and water contact angle measurement were performed to characterize the morphological characteristic, chemical composition and superhydrophobicity of the surfaces. The as-prepared superhydrophobic surfaces showed a water contact angle as high as ca.160° and sliding angle as low as ca.3°. We hope the method to produce superhydrophobic surface can be used in many fields.

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ZHAN Conghong, CHENG Rongmin, FANG Beibei, ZHAO Lijun
Shape-controlled Synthesis of Fe3O4 Nanocrystals with Incontinuous Multicavities
2016 Vol. 32 (2): 159-164 [Abstract] ( 29 ) [HTML 1KB] [PDF 0KB] ( 36 )   
doi: 10.1007/s40242-016-5383-4

In the solvothermal synthesis process, the effect of NaOH dosages of from 0.3 g to 4.0 g on the morphology evolution(from nanoparticles to octahedra) of Fe3O4 crystals was carefully investigated. Meanwhile, the growth process of Fe3O4 crystals at different reaction time was also investigated. Furthermore, it has been found that the particle size and crystallinity of Fe3O4 crystals can be controlled by the dosages of NaOH. In this paper, the increases of both the reaction time and the NaOH concentrations correspond to a minimization process of surface energy for Fe3O4 crystals. During the synthesis process, the addition of N2H4·H2O and ethylene glycol in the magnetite not only facilitated the narrow distribution of particle size but also contributed to the formation of incontinuous multicavities with a diameter of about 5 nm.

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ZHANG Qingfen, ZHOU Zhongyuan, WANG Xuan, LU Jing
Syntheses, Structures and Magnetic Properties of Two Coordination Polymers Based on 2, 2-Biphenyldicarboxylate Ligand
2016 Vol. 32 (2): 165-171 [Abstract] ( 41 ) [HTML 1KB] [PDF 0KB] ( 61 )   
doi: 10.1007/s40242-016-5365-6

Two coordination polymers {[Co3L3(Me2NH)2]·(Me2NH)}n(1) and [CuL(bpy)]n(2)(L=2,2'-biphenyl dicarboxylate ion, bpy=4,4'-bipyridine) were obtained and characterized. Compound 1 was synthesised via solvothermal method, with the L ligands adopting syn-syn-μ2-η1:η1- and μ2-η2-coordination modes and Co(II) centers being linked to form a 1D coordination chain with trinuclear Co3 cluster as sub-units. Compound 2 was synthesized at room temperature, with the L ligand chelating the Cu(II) centers to form a 1D chain, which was further linked by the auxiliary 4,4'-bpy ligand to form a 3D coordination network. The results of variable temperature susceptibility studies reveal that there were ferromagnetic and antiferromagnetic interactions between the paramagnetic metal centers in compounds 1 and 2, respectively.

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SONG Shengmei, MA Xuewen, ZHOU Yehong, XU Maotian, SHUANG Shaomin, DONG Chuan
Studies on the Interaction Between Vanillin and β-Amyloid Protein via Fluorescence Spectroscopy and Atomic Force Microscopy
2016 Vol. 32 (2): 172-177 [Abstract] ( 20 ) [HTML 1KB] [PDF 0KB] ( 53 )   
doi: 10.1007/s40242-016-5347-8

β-Amyloid(Aβ) plaques and intracellular neurofibrillary lesions in the brain are markers of Alzheimer's disease(AD). The ability to safely decrease Aβ concentrations is potentially important as a preventive strategy for AD. The interactions between vanillin and Aβ polypeptide were investigated via fluorescence spectroscopy and atomic force microscopy(AFM). The results of fluorescence and synchronous spectroscopies illustrate that the intrinsic fluorescence of tyrosine(Tyr) residues in Aβ1-42 aggregates can be quenched strongly upon the formation of vanillin-Aβ1-42 complex. Thioflavine T(ThT)-induced fluorescence changes indicated that Aβ1-42 aggregates could be disaggregated by vanillin, and the AFM images of Aβ1-42 enunciated the depolymerization of Aβ1-42 aggregates by vanillin in a dose-dependent manner. Vanillin may be a potential pharmacological agent for the treatment of AD.

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UANSIRI Sutthirak, VICHAPONG Jitlada, KANCHANAMAYOON Wanna
Ultrasound-assisted Low Density Solvent Based Dispersive Liquid-liquid Microextraction for Determination of Phthalate Esters in Bottled Water Samples
2016 Vol. 32 (2): 178-183 [Abstract] ( 10 ) [HTML 1KB] [PDF 0KB] ( 48 )   
doi: 10.1007/s40242-016-5343-z

A technique of ultrasound-assisted low density solvent based dispersive liquid-liquid microextraction was developed for the determination of four phthalate esters, including dimethyl phthalate(DMP), diethyl phthalate(DEP), di-n-butyl phthalate(DnBP) and di(2-ethylhexyl) phthalate(DEHP) in bottled water samples. A low density solvent, toluene, was selected as extraction solvent. In the extraction process, a mixture of 15 μL of toluene(extraction solvent) and 100 μL of methanol(disperser solvent) was rapidly injected into 1.0 mL of water samples. A cloudy solution was formed after ultrasounded for 5 min, and then centrifuged at 5000 r/min for 5 min. The enriched analytes in the floating phase were determined by means of gas chromatograph. Under the optimum conditions, the enrichment factors were found to be in a range of 29-67, and the recoveries were ranged from 81.2% to 103.9%. The limits of the detection were in a range of 3.8-5.6 μg/L. The proposed method was applied to the extraction and determination of phthalate esters in bottled water samples, and the concentrations of phthalate esters found in the water samples were below the allowable levels.

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ZHENG Tianxing, HAN Yide, LIU Ningning
A Cobalt Supramolecular Compound Constructed from 4, 6-Di(1-imidazolyl)-1, 3, 5-triazine-2-one: Synthesis, Characterization and Magnetic Property
2016 Vol. 32 (2): 184-187 [Abstract] ( 24 ) [HTML 1KB] [PDF 0KB] ( 32 )   
doi: 10.1007/s40242-016-5456-4

A cobalt(II) coordination polymer, [Co(dimto)2(H2O)2]·4H2O[1, dimto=4,6-di(1-imidazolyl)-1,3,5-triazine-2-one], has been prepared under solvothermal condition. Single-crystal structural analysis reveals that compound 1 crystallizes in the orthorhombic space group Ibca(No.73) with a=1.80696(12) nm, b=1.93224(11) nm, c=1.36798(10) nm, V=4.7763(5) nm3 and R1=0.0438. Compound 1 is a 3D supramolecular architecture composed of 1D wave-like chains with hydrogen bonds and π-π interactions. Compound 1 was further characterized by powder X-ray diffraction(PXRD), infrared(IR) spectroscopy, thermogravimertic analysis(TG) and elemental analysis. Additionally, the magnetic property of compound 1 was also investigated.

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LIU Qixing, HUANG Mingzhi, LIU Aiping, HU Aixi, LEI Manxiang, REN Yeguo, HUANG Lu
Synthesis and Herbicidal Activity of Novel N-Allyloxy/Propargyloxy Aryloxyphenoxy Propionamide Derivatives
2016 Vol. 32 (2): 188-194 [Abstract] ( 17 ) [HTML 1KB] [PDF 0KB] ( 38 )   
doi: 10.1007/s40242-016-5415-0

A series of novel N-allyloxy/propargyloxy aryloxyphenoxy propionamide compounds was designed and prepared. The structures of the synthesized compounds were confirmed by means of 1H NMR, 13C NMR, LC-MS, elemental analysis and IR. The bioassay results indicate that when against Digitaria sanguinalis and Echinochloa crus-galli, (R)-N-(propargyloxy)-2-{4-[(6-chloroquinoxalin-2-yl)oxy]phenoxy}propanamide(1m)(IC50=6.8 and 6.5 g/hm2, respectively) and (R)-N-(allyloxy)-2-{4-[(6-chloroquinoxalin-2-yl)oxy]phenoxy}propanamide(1r)(IC50=7.4 and 6.0 g/hm2, respectively) are much more effective than commercial aryloxyphenoxypropionic ester herbicide clodinafop-propargyl(IC50=46.5 and 14.6 g/hm2, respectively). The results of crop selectivity show that compounds 1m and 1r are safe to soybean, rape and cotton and can be used as herbicides for soybean, rape and cotton crop.

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WEI Wei, CHENG Dandan, CHEN Wei, LIU Jingbo, WAN Yingying, LI Yuxin, LI Yonghong, YU Shujing, LI Zhengming
Design, Syntheses and Biological Activities of Novel Sulfonylureas Containing an Oxime Ether Moiety
2016 Vol. 32 (2): 195-201 [Abstract] ( 16 ) [HTML 1KB] [PDF 0KB] ( 48 )   
doi: 10.1007/s40242-016-5406-1

Since sulfonylurea is one of the most potent acetohydroxyacid synthase(AHAS) inhibitors, a series of novel sulfonylureas containing an oxime ether moiety was designed and synthesized and their chemical structures were determined by means of 1H nuclear magnetic resonance(NMR), 13C NMR and high-resolution mass spectrometry(HRMS). In the herbicidal bioassay, several compounds showed moderate to good herbicidal activities against dicotyledons, but their activities against monocotyledons decreased. The in vitro antifungal activity was tested at a dosage of 50 mg/L. And the results show that compounds 7l, 7m and 7n exhibit promising antifungal activities against six common plant pathogenic fungi. Further investigations on molecular modification are in progress.

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LIU Lijing, GUO Lei, ZHAO Qiuhua, SHAN Yongkui, LIAO Xiaojuan
Effect of Alkylpyrazinium Counterions on the Host-guest Recognition Based on Dimethoxypillar[5]arenes
2016 Vol. 32 (2): 202-206 [Abstract] ( 27 ) [HTML 1KB] [PDF 0KB] ( 52 )   
doi: 10.1007/s40242-016-5402-5

In this work, we synthesized n-octylpyrazinium bromide(G-Br) and n-octylpyrazinium hexafluorophosphate(G-PF6) as model guests and studied their host-guest complexation with 1,4-dimethoxypillar[5]arene(DMP5A). Effect of alkylpyrazinium counterions on the host-guest recognition was investigated. Based on the 1H NOESY spectra, the binding site of DMP5A with G-PF6 is the same as that of DMP5A with G-Br. However, G-PF6 forms a stronger complex with DMP5A than G-Br, owing to that hexafluorophosphate forms weaker doubly inonic H-bonds with ammonium cation than bromide ion in chloroform, which leads to some aggregates that could be dissociated with the addition of DMP5A.

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LI Chuanhua, JIANG Jianhong, LI Xu, XIAO Shengxiong, WEI Deliang, JIANG Chao, XIE Jinqi, PENG Mengna, GU Huiwen, LI Qiangguo
Synthesis and Bioactivity of a Novel Bismuthoxide Schiff-base Complex Derived from Salen-like Ligand and Bismuth(Ⅲ) Nitrate
2016 Vol. 32 (2): 207-211 [Abstract] ( 17 ) [HTML 1KB] [PDF 0KB] ( 53 )   
doi: 10.1007/s40242-016-5350-0

In this paper, a novel bismuthoxide Schiff-base complex [Bi9O8(vanen)3(NO3)2(CH3OH)2(H2O)·3NO3·5.5H2O](abbreviated as Bivanen) was synthesized with Salen-like ligand H2vanen[H2vanen=N,N'-ethylene bis(3-methoxysalicylideneimine)] and bismuth(Ⅲ) nitrate. Its structure was characterized by IR spectra, NMR spectra and X-ray diffraction. In particular, the biology activities of the ligand and the complex against Schizosaccharomyces pombe(S. pombe) were studied using biological microcalorimetry. The metabolic thermogenic curves of S. pombe were measured at 32.00℃. Then, some quantitative thermokinetic parameters of growth metabolism of S. pombe including the rate constant(k), inhibition ratio(I) and half inhibition concentration(IC50) were calculated. Experimental results showed that the k values of S. pombe decreased while I values of S. pombe increased with the increase of concentrations of the ligand and the complex. The IC50 of the ligand and the complex were found to be 0.067 and 0.037 mmol/L, respectively.

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LÜ Guanghui, CHENG Xu, ZHENG Yang, LI Weijian, HAI Li, WU Yong
Benzoic Acid: an Efficient and Rapid Catalyst for the Synthesis of α-Hydroxyl(indolyl)ethanones from Indoles
2016 Vol. 32 (2): 212-218 [Abstract] ( 24 ) [HTML 1KB] [PDF 0KB] ( 36 )   
doi: 10.1007/s40242-016-5301-9

An efficient method for regioselective Friedel-Crafts alkylations of indole using arylglyoxals in the presence of benzoic acid has been discovered. The reactions proceeded smoothly at room temperature under metalfree conditions and generated the corresponding products in good to excellent yields. This methodology has a broad substrate scope and opens up an interesting and attractive avenue for the synthesis of α-hydroxyl(indolyl)-ethanones.

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CHEN Feng, LU Cuifen, NIE Junqi, CHEN Zuxing, YANG Guichun
Scope and Limitations of Optical Pure Hydantoins as Chiral Auxiliaries in Asymmetric Mannich Reactions
2016 Vol. 32 (2): 219-225 [Abstract] ( 10 ) [HTML 1KB] [PDF 0KB] ( 57 )   
doi: 10.1007/s40242-016-5273-9

The Mannich reaction of various 5-substituted and N-acyl substituted chiral hydantoins with a series of aldimines smoothly occurred with full stereochemical control. These Mannich adducts have been cleaved by alcoholysis to afford several synthetically useful chiral building blocks like β-amino esters and β-lactams in good yields and in enantiopure form.

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PENG Li, XIA Xu, LIU Xipeng
Biochemical Characterization of Translesion Synthesis by Sulfolobus acidocaldarius DNA Polymerases
2016 Vol. 32 (2): 226-233 [Abstract] ( 39 ) [HTML 1KB] [PDF 0KB] ( 49 )   
doi: 10.1007/s40242-016-5337-x

To study the DNA synthesis mechanism of Sulfolobus acidocaldarius, a thermophilic species from Crenarchaeota, two DNA polymerases of B family(polB1 and polB3), and one DNA polymerase of Y family(polIV) were recombinantly expressed, purified and biochemically characterized. Both DNA polymerases polB1(Saci_1537) and polB3(Saci_0074) possessed DNA polymerase and 3' to 5' exonuclease activities; however, both the activities of B3 were very inefficient in vitro. The polIV(Saci_0554) was a polymerase, not an exonuclease. The activities of all the three DNA polymerases were dependent on divalent metal ions Mn2+ and Mg2+. They showed the highest activity at pH values ranging from 8.0 to 9.5. Their activities were inhibited by KCl with high concentration. The optimal reaction temperatures for the three DNA polymerases were between 60 and 70℃. Deaminated bases dU and dI on DNA template strongly hindered primer extension by the two DNA polymerases of B family, not by the DNA polymerase of Y family. DNA polymerase of Y Family bypassed the two AP site analogues dSpacer and propane on template more easily than DNA polymerases of B family. Our results suggest that the three DNA polymerases coordinate to fulfill various DNA synthesis in Sulfolobus acidocaldarius cell.

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LIU Jianhong, LÜ Cunqin, JIN Chun, GUO Yong, WANG Guichang
Density Functional Theoretical Studies on the Methanol Adsorption and Decomposition on Ru(0001) Surfaces
2016 Vol. 32 (2): 234-241 [Abstract] ( 14 ) [HTML 1KB] [PDF 0KB] ( 43 )   
doi: 10.1007/s40242-016-5416-z

Periodic density functional theory(DFT) calculations are presented to describe the adsorption and decomposition of CH3OH on Ru(0001) surfaces with different coverages, including p(3×2), p(2×2), and p(2×1) unit cells, corresponding to monolayer(ML) coverages of 1/6, 1/4, and 1/2, respectively. The geometries and energies of all species involved in methanol dissociation were analyzed, and the initial decomposition reactions of methanol and the subsequent dehydrogenations reactions of CH3O and CH2OH were all computed at 1/2, 1/4, and 1/6 ML coverage on the Ru(0001) surface. The results show that coverage exerts some effects on the stable adsorption of CH3O, CH2OH, and CH3, that is, the lower the coverage, the stronger the adsorption. Coverage also exerts effects on the initial decomposition of methanol. C-H bond breakage is favored at 1/2 ML, whereas C-H and O-H bond cleavages are preferred at 1/4 and 1/6 ML on the Ru(0001) surface, respectively. At 1/4 ML coverage on the Ru(0001) surface, the overall reaction mechanism can be written as 9CH3OH→3CH3O+6CH2OH+9H→6CH2O+3CHOH+18H→7CHO+COH+CH+OH+26H→8CO+C+O+36H.

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WANG Juan, SUN Runguang, LI Junhua
Influence of K+, Na+ or Ca2+ Ions on the Interaction Between AmB and Saturated Phospholipids by Langmuir Technique
2016 Vol. 32 (2): 242-247 [Abstract] ( 5 ) [HTML 1KB] [PDF 0KB] ( 21 )   
doi: 10.1007/s40242-016-5410-5

Interaction between amphotericin B(AmB) and cell membrane is influenced by different metal cations. In the presence of K+, Na+ or Ca2+ ions, the surface pressure-area isotherms and the elastic modulus of an amphotericindipalmitoylphosphatidylcholine(AmB-DPPC) mixed monolayer were discussed. And the excess free energy and entropies of mixing were calculated according to the surface pressure-area isotherms. The phase transition of the mixed monolayer needed a higher concentration of AmB in the sequence Na+ > pure buffer > K+ > Ca2+. When the molar fraction of AmB(xAmB) was 0.5, the molecular interaction changed from attraction to repulsion and the mixed monolayer turned to ordered state from disorder state under the induction of K+ or Ca2+ ions at all surface pressure in our experiment. At high surface pressure, the disorder of monolayer enhanced in the presence of Na+ ions at xAmB > 0.1. At different molar ratios of AmB, the influences of these metal cations were discrepant. These cations may influence AmB molecules to form pores on the monolayer. It is helpful to understand the reduction of AmB's toxicity as theoretical reference.

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DONG Weili, ZHANG Xiyan, SHI Hui, WANG Nengli, ZHANG Wenmin, LI Liang, XUE Qingxue
Preparation and Luminescence Properties of Color-tunable Single-phased LaPO4: Eu3+/Tb3+ Phosphors
2016 Vol. 32 (2): 248-252 [Abstract] ( 11 ) [HTML 1KB] [PDF 0KB] ( 26 )   
doi: 10.1007/s40242-016-5407-0

A novel series of color-tunable single-phased phosphors La1-x-yPO4:xEu3+/yTb3+(x=0, 0.01, 0.02, 0.03, 0.04, 0.05; y=0, 0.05, 0.10, 0.15, 0.20) was synthesized via microwave-assisted co-precipitation method with diammonium hydrogen phosphate as precipitant. The morphology, crystal structure and photoluminescence properties of the as-prepared samples were characterized by means of X-ray diffraction(XRD), scanning electron microscopy(SEM) and fluorescence spectrophotometer. The results reveal that the as-synthesized samples calcined at 1100℃ display spherical morphology with uniform distribution. Upon excitation with 350 nm ultraviolet radiation, the LaPO4:Eu3+/Tb3+ phosphors showed a green light peaking at 543 nm assigned to the characteristic 5D4-7F5 emission of Tb3+ and a red light peaking at 591 nm corresponding to the characteristic 5D0-7F1 emission of Eu3+ simultaneously. For the Eu3+/Tb3+ co-activated phosphors, Tb3+ acts as an efficient sensitizer to enhance the emission intensity of Eu3+ ions. The energy transfer mechanism and the emission color tunability of LaPO4:Eu3+/Tb3+ have been studied. The results indicate that a color-tunable luminescence(from green to white to red) can be achieved by adjusting the Eu3+/Tb3+ doping ratio in the LaPO4 host matrix.

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Melek HAJJI, Taha GUERFEL
Crystal Structure, Vibrational Studies, Optical Properties and TG-DTA Investigations of a New Chlorocadmate Templated by 1-Methylimidazolium
2016 Vol. 32 (2): 253-260 [Abstract] ( 19 ) [HTML 1KB] [PDF 0KB] ( 21 )   
doi: 10.1007/s40242-016-5404-3

Chemical preparation, X-ray single crystal diffraction, thermal analysis, electrochemical measurements, IR, Raman and UV spectroscopic investigations of a novel organic-inorganic hybrid material(C4H7N2)CdCl3(H2O)(1) were described. 1-Methylimidazolium aquapentachlorocadmate(II) crystallized in the monoclinic system with P21/n space group. Its structure provided a new interesting example of infinite inorganic layers of [CdCl3(H2O)]nn- centered by (-101) planes. The [CdCl5(H2O)]-anions were interconnected by O-H···Cl hydrogen bonds. Acidic protons of the chloride group were transferred to the organic molecule, giving the singly-protonated cations. The ability of ions to form a spontaneous three-dimensional structure through O-H···Cl and N-H···Cl hydrogen bonds was fully utilized. These hydrogen bonds induced notable vibrational effects. IR and Raman spectra were reported and discussed on the basis of group theoretical analysis and on quantum chemical density theory(DFT) calculation. The molecular HOMO-LUMO compositions and their respective energy gaps were also drawn to explain the activity of our compound. The role of the intermolecular interaction in this crystal was analyzed. The optical study was also investigated by UV-Vis absorption spectrum. Thermal analysis reveals the hydrous character of the compound. Cyclic voltammetry was studied to evaluate the spectral and structural changes accompanying electron transfer.

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CHEN Tao, SUN Chengxun
Polychlorinated Biphenyls-contaminated Soil Washing with Mixed Surfactants Enhanced by Electrokinetics
2016 Vol. 32 (2): 261-267 [Abstract] ( 16 ) [HTML 1KB] [PDF 0KB] ( 52 )   
doi: 10.1007/s40242-016-5369-2

On the basis of comparing the adsorption loss of different surfactants[single nonionic surfactant sorbitanmonooleatepolyoxyethylene ether(Tween 80), anionic surfactant sodium dodecyl benzene sulfonate(SDBS), and mixed surfactants Tween 80/SDBS(3:2), Tween 80/SDBS(4:1)] and their performance in the enhancement of polychlorinated biphenyls(PCBs) desorption from soil, the impact of electric field intensity on the desorption of PCBs and the transport of surfactants in washing resulted solution were investigated in this study. With regard to the remediation cost, 1000 mg/L mixed Tween 80/SDBS(3:2) was recognized as an optimum concentration in the remediation of PCBs-contaminated soil, because Tween 80/SDBS(3:2) had the highest washing capacity and relatively low adsorption loss onto soil. Electrokinetics can enhance the washing efficiency of PCBs-contaminated soil by Tween 80/SDBS(3:2) effectively and safely at an electric field intensity of 1.5 V/cm for 10 d, for the desorption of PCBs was 1.57 times more than that without electrokinetics, and the most of organic residue in washing resulted solution was removed in an electrical field to avoid the possible secondary contamination risk.

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WANG Yang, ZHAO Zengxia, ZHANG Hongxing
Ethynyl Substitution Effect on the Electronic Excitation Spectra of Aniline
2016 Vol. 32 (2): 268-271 [Abstract] ( 8 ) [HTML 1KB] [PDF 0KB] ( 24 )   
doi: 10.1007/s40242-016-5355-8

We made an extended study on the structure and properties of the low-lying electronic states of ethynyl substituted aniline and their cations. We performed these calculations using density functional theory method(B3LYP and CAM-B3LYP DFT) and the complete active space self-consistent field(CASSCF) approach in connection with the aug-cc-pVZ Dunning's basis sets and concerted ANO-L-VDZP basis sets. Our results included their equilibrium geometries, the vertical excitation spectra and the vertical and adiabatic ionization energies. The effect of ethynyl substitution on the electronic structure and the spectroscopy of aniline was probed.

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LIU Jun, LAN Lixin, WU Chao, LI Rong, LIU Xuanyan
Agglomerated Pd Catalysts and Their Applications in Hydrogen Production from Formic Acid Decomposition at Room Temperature
2016 Vol. 32 (2): 272-277 [Abstract] ( 7 ) [HTML 1KB] [PDF 0KB] ( 27 )   
doi: 10.1007/s40242-016-5331-3

Agglomerated Pd catalysts with the nano-porous structure were simply prepared by one-step reduction reaction without using any stabilizer. The Pd catalysts show a high catalytic activity for the decomposition of formic acid at room temperature. Among all the Pd catalysts tested, the PdMg catalyst exhibits the highest catalytic activity. Moreover, the breakthrough of the advanced catalysts is that the above agglomerated Pd catalysts can be easily separated from the liquid system to control the catalytic reaction at any time, which may further promote the practical application of formic acid as a H2 storage material.

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CHEN Bin, CHEN Jie, YANG Liming, ZHAO Guochen, DING Guowei
Functional β-Cyclodextrin Coating by Electrodeposition on Stainless Steel for Drug Loading and Release
2016 Vol. 32 (2): 278-283 [Abstract] ( 4 ) [HTML 1KB] [PDF 0KB] ( 42 )   
doi: 10.1007/s40242-016-5328-y

β-Cyclodextrin(β-CD) can be used for drug loading and release in biomedical application. β-Cyclodextrinsalicylate(β-CD-S) was synthesized by transesterification and then was electrodeposited on the surface of stainless steel(SS) by the anodic electrooxidation polymerization of the salicylate. 1H NMR spectrometry was used to determine the structure of β-CD-S. FTIR spectroscopy and XPS were applied to verifying the synthesized β-CD-S and the existence of the electrodeposited layer on the SS surface, respectively. Tafel plots and electrochemical impedance spectroscopy(EIS) technologies were used to estimate the corrosion resistance of β-CD-covered stainless steel. Electrochemical quartz crystal microbalance was applied to determining the drug loading of the stainless steel before and after its modification. E. coli was selected as a harmful microbe to evaluate the antibacterial properties of the stainless steel with the comparison of optical density values.

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LIU Yujun, ZHOU Feng, ZHAN Su, YANG Yifan, YIN Yanfeng
Significantly Enhanced Performance of g-C3N4/Bi2MoO6 Films for Photocatalytic Degradation of Pollutants Under Visible-light Irradiation
2016 Vol. 32 (2): 284-290 [Abstract] ( 45 ) [HTML 1KB] [PDF 0KB] ( 53 )   
doi: 10.1007/s40242-016-5315-3

The films of photocatalysts have been widely used in decomposition pollutants. In this study, the films were successfully prepared from Bi2MoO6 and g-C3N4/Bi2MoO6 by a simple method, respectively. The samples were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), Fourier transform infrared spectroscopy(FTIR), photoluminescence(PL), UV-Vis diffuse reflectance spectroscopy(DRS) and electrochemical experiments to investigate crystalline structure, morphology, composition and properties. The photocatalytic activity of the photocatalyst films for the pollutants was evaluated by degradation of methylene blue(MB) in aqueous solution under visible light irradiation. Experiments revealed that the film of g-C3N4/Bi2MoO6 exhibited higher photocatalytic ability compared to the single-component photocatalyst, and proved its stability. The superior catalytic performance can be attributed to the effective separation of electron-hole pairs and the reduced rate of recombination. This work is of great value for the preparation of photocatalysts films.

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XIANG Zheng, ZHAO Xueping, GE Junjie, MA Shuhua, ZHANG Yuwei, NA Hui
Effect of Sulfonation Degree on Performance of Proton Exchange Membranes for Direct Methanol Fuel Cells
2016 Vol. 32 (2): 291-295 [Abstract] ( 7 ) [HTML 1KB] [PDF 0KB] ( 42 )   
doi: 10.1007/s40242-016-5344-y

A series of proton exchange membranes based on sulfonated polyarylene ether ketones(SPAEKs) was used to study the effect of sulfonation degree on proton conductivity, methanol permeation and performance of direct methanol fuel cells(DMFCs). Dependences of physical characteristics of the membranes, i. e., proton conductivity, water uptake, swelling ratio, methanol permeability and ion exchange capacity(IEC) were systematically studied. Both methanol permeability and proton conductivity of the SPAEK membrane grow rapidly as the increase in sulfonation degree since methanol molecules and protons share the same transfer channel. However,the methanol permeability plays more important role comparing to proton conductivity. As a result, the SPAEK membrane with a medium sulfonation degree(60%) was found to yield the best performance in a DMFC due to the acquirement of balanced conductivity and methanol permeability.

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LIU Bo, QIAO Wenqiang, WANG Zhi Yuan
Intense Near- and Mid-infrared Absorbing Films of Electrochemically Crosslinked Multinuclear Metallodithiolene Complex Polymers
2016 Vol. 32 (2): 296-301 [Abstract] ( 5 ) [HTML 1KB] [PDF 0KB] ( 21 )   
doi: 10.1007/s40242-015-5309-6

Novel multinuclear metallodithiolene complexes [(Cbz)2-BTT-Pd(dppf)]2Ni[6b, Cbz=carbazole, BTT=benzene-1,2,4,5-tetrathiotate, dppf=1,1'-bis(diphenylphosphino) ferrocene] and polymer [(Cbz)2-BTT-Ni]n·[(Et)3(PhCH2)N]x(7b) with the carbazole pendent groups were synthesized and characterized. The thin films of crosslinked polymers P6b and P7b were prepared by electrochemical polymerization of compounds 6b and 7b, respectively. These films show intense and broad absorption in the near- and mid-infrared spectral regions(P6b: 1000-1600 nm, λmax=1297 nm; P7b: 800 nm-8 μm, λmax=3.9 μm) and are potentially useful as infrared optical materials.

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LIU Yabo, XU Yihan, ZHAO Yaru, JIA Yuxi
Effect of Ionic Concentration on Drug Release from Polyelectrolyte Hydrogel Carriers Analyzed via Triphasic Mechanism Model
2016 Vol. 32 (2): 302-310 [Abstract] ( 20 ) [HTML 1KB] [PDF 0KB] ( 39 )   
doi: 10.1007/s40242-015-5295-8

In different parts of the gastrointestinal tract, the rate of drug release from polyelectrolyte hydrogel tablets is highly affected by variance of ionic concentration. This research aims at revealing clearly how the drug release from a hydrogel matrix is affected by ionic concentration of external solution through the finite element simulation and triphasic mechanism model. The coupled relationship of the motions including the polyelectrolyte hydrogel swelling, the water flow and the ion diffusion, is illustrated in the present work. In order to simulate the drug controlled release from a swollen polyelectrolyte hydrogel carrier, the mathematical model was built on the basis of the multiphasic theory of polyelectrolyte hydrogels. Finally, the reliability of the simulation method was verified qualitatively by experimental results. The results reveal that when the initial concentration of fixed anions of polymer network is higher than the concentration of free anions in the external solution, the drug release rate increases with increasing the ionic concentration of the external solution. The research is helpful for the optimal design of oral drug release in gastrointestinal tract.

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WANG Honglei, LIU Weiqu, TAN Jianquan, XIAHOU Guolun
Synthesis and Characterization of Novel UV-curable Fluorinated Polyurethane-acrylate Copolymer
2016 Vol. 32 (2): 311-317 [Abstract] ( 24 ) [HTML 1KB] [PDF 0KB] ( 27 )   
doi: 10.1007/s40242-016-5272-x

A series of UV-curable fluorinated polyurethane-acrylate(PUA) has been developed by incorporating octafluoropentyl alcohol into the segment of UV-curable polyurethane-acrylate to improve the thermal property and surface property of the copolymer material. The structures of the synthesized polymers were characterized by Fourier transform infrared(FTIR) spectrometry. In order to find out the effect of incorporated fluorine on the UV-cured films, the properties of the UV-cured films were tested through contact angle, water absorption, and thermogravimetric analysis (TGA). The fractured-surface morphologies of the UV-cured coatings were investigated by scanning electron microscopy(SEM). With increasing the content of fluorine segments, the contact angle of the UV-cured films increased and the water absorption decreased, suggesting the fluorine segments migrated and formed a fluorine-covered surface to avoid water penetration. The observation of the fractured-surface morphology through SEM test showed that the fluorinated UV-cured films gained rough fractured-surface compared with the pure UV-cured polyacrylate film, demonstrating the migrating of the fluorine segments. The TGA curves show that the fluorinated UV-cured films gained higher thermal degradation temperature than the virgin UV-cured polyacrylate film. And as increasing the fluorine content, the thermal degradation temperature increased. These phenomena could be reasonably explained by the enrichment of fluorinecontained segment on the surface of the film and the high thermal property due to fluorine atom.

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MIAO Shoulei, ZHANG Haiqiu, CHEN Zhimin, WANG Bin, LI Xiaobo, WU Yiqun
Sulfonated Polyarylene Ether Sulfone (SPES) and Ga2O3 Based Hybrid Polymer Electrolyte Membrane for Direct Methanol Fuel Cells (DMFCs)
2016 Vol. 32 (2): 318-324 [Abstract] ( 13 ) [HTML 1KB] [PDF 0KB] ( 45 )   
doi: 10.1007/s40242-016-5362-9

Novel hybrid polymer electrolyte membrane, based on sulfonated polyarylene ether sulfone(SPES) and Ga2O3, was prepared and characterized. The structure of the composite membrane substantially modified the properties of SPES in terms of thermal stability, mechanical properties, methanol permeability, and so on. The structure and performance of the hybrid membrane were investigated by means of Fourier transform infrared spectrophotometry(FTIR), scanning electron microscopy(SEM), electrochemical impedance spectroscopy(EIS), thermal gravimetric analysis(TGA), and water uptake(WU) test. The hybrid polymer electrolyte membrane containing a certain quantity of Ga2O3 was found to gain good proton transport characteristics, particularly at relatively high temperatures. In addition, this membrane reduced methanol permeability and improved thermal stability in comparison to an unfilled reference membrane. The hybrid membrane was found suitably to be used as a polymer electrolyte membrane(PEM) in direct methanol fuel cells(DMFCs).

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