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2016 Vol.32 No.4
 Published: 01 August 2016

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Chemical Research in Chinese Universities Vol.32 No.4 August 2016
2016 Vol. 32 (4): 0-0 [Abstract] ( 11 ) [HTML 1KB] [PDF 2209KB] ( 16 )   

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Nabaa BOUZIDIA, Besma HAMDI, Abdelhamid BEN SALAH
A New Non-centrosymmetric Microporous Fluorinated Iron Phosphate: Structural Elucidation, Spectroscopic Study and Hirshfeld Surface Analysis
2016 Vol. 32 (4): 519-526 [Abstract] ( 25 ) [HTML 1KB] [PDF 0KB] ( 2 )   
doi: 10.1007/s40242-016-6012-y

The crystal structure of a new non-centrosymmetric microporous fluorinated iron phosphate, (H3O)2[Fe4(H2O)2F4(PO4)2(HPO4)2](H2O), was determined by single crystal X-ray diffraction analysis and the result reveals that it belongs to the orthorhombic system with four molecules in the unit cell(space group P212121). Thus, the complex was characterized by powder X-ray diffraction, spectroscopic techniques(Fourier transform infrared and Fourier transform Raman) and 19F MAS NMR. The elemental analysis of the sample was also carried out. The chiral inorganic sheets, which stacked along[100] showed the presence of FeF2O4 as well as FeF2O3H2O octahedra, PO4 besides HPO4 tetrahedra, hydronium ions(H3O+) and isolated water molecules. Hirshfeld surface analysis, especially dnom surface and fingerprint plots, were used for decoding the intermolecular interactions in the crystal network and the contribution of component units for the construction of the 3D architecture. From the Hirshfeld surfaces and 2D fingerprint analysis, it was found that the subtle interactions, such as H…H associating the third intense interaction of all intercontacts, provide extra stabilization in addition to the presence of the strong hydrogen bonds mentioned above.

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GAI Beibei, HE Hui, ZHAO Yanhui, MAO Zhu, FU Hai
Ionothermal Synthesis and Characterization of Two Polyoxometalate-based Supramolecules
2016 Vol. 32 (4): 527-529 [Abstract] ( 37 ) [HTML 1KB] [PDF 0KB] ( 52 )   
doi: 10.1007/s40242-016-6058-x

Two novel 3D supramolecular architectures with hexamolybdate and phosphotungstate anions were synthesized under ionothermal conditions. The structures were named as[CuI(L1)2]2L2[Mo6O19](1) and[CuI(L3)2]2.5· H0.5[PW12O40]·H2O(2)(L1=2,2'-bipyridine, L2=4,4'-bipyridine, L3=2,2'-biimidazole) and characterized via Fourier transform infrared spectroscopy(FTIR) and FT-Raman spectroscopy analyses. Single-crystal X-ray diffraction analysis revealed that the two compounds crystallized in the space group P and were constructed through hydrogen bonding.

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ZHANG Meng, TU Xianneng, WANG Jingyang, FANG Tuo, WANG Yanli, XU Xiaodong, ZHANG Milin, CHEN Yitung
Hydrothermal Syntheses of CuO, CuO/Cu2O, Cu2O, Cu2O/Cu and Cu Microcrystals Using Ionic Liquids
2016 Vol. 32 (4): 530-533 [Abstract] ( 26 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-016-6037-2

In this paper, CuO, CuO/Cu2O, Cu2O, Cu2O/Cu and Cu microcrystals were synthesized via a hydrothermal method by mixing Cu(NO3)2·3H2O and NaOH together in the presence of an ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate([BMIM]BF4) or 1-butyl-3-methylimidazolium chloride([BMIM]Cl). The structures and the morphologies of the obtained products were characterized by means of X-ray diffractometer(XRD), field-emission scanning electron microscopy/energy-dispersive spectroscopy(FESEM/EDS), transmission electron microscopy/selected area electron diffraction(TEM/SAED) and Raman spectroscopy. The result of XRD indicates that Cu2O and Cu microcrystals are cubic phase and the Raman spectra confirm the presence of carbon. The results of FESEM and TEM images show Cu2O microcrystals as rule cubes of 2 μm in length and Cu particles of 5 μm in diameter. According to the difference between crystal structures, bi-component and single component products were synthesized by adjusting the reaction conditions. A possible formation mechanism of Cu2O and Cu was proposed in[BMIM]BF4.

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ZHANG Lei, LI Hongfeng, CHEN Peng, SUN Wenbin, YAN Pengfei
Quadruple-stranded Eu-helicate Assembled from Bis-β-diketonate: Its Stability Towards Metal Ions
2016 Vol. 32 (4): 534-538 [Abstract] ( 33 ) [HTML 1KB] [PDF 0KB] ( 4 )   
doi: 10.1007/s40242-016-6009-6

Herein, we reported the synthesis and investigation of highly luminescent quadruple-stranded helicate (C6H16N)4[Eu2(MBDA)4]2.3C4H10O·4C2H3N(1-Eu)[H2MBDA=N-methyl-4,4'-bis(4,4,4-trifluoro-1,3-dioxobutyl)di- phenylamine] for its stability toward metal ions in the solution. The material was characterized via X-ray crystallographic technique, Fourier transform infrared(FTIR) spectroscopy and electrospray ionization quadrupole time-of- flight(ESI-TOF) mass spectrometry. The results on the luminescence quantum yields clearly demonstrate that the ligand can effectively sensitize the luminescence of the Eu3+ ions(Φoverall=15%). Upon the addition of different metal ions(i. e., Ag+, Cd2+, Zn2+, Fe3+, Al3+ and Ni2+) to the CH3CN solution of compound 1-Eu, the emission intensities of Eu3+ ions at 612 nm were affected to some extent, which could be attributed to the presence of ion exchanges between Eu3+ ions and the metals ions, and the result was confirmed by ESI-TOF mass spectrometry.

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WANG Xiaofang, SONG Qingshan, PAN Ying, QIU Shilun, XUE Ming
Two New Cadmium Metal-organic Frameworks Based on a Mixed-donor Ligand
2016 Vol. 32 (4): 539-544 [Abstract] ( 46 ) [HTML 1KB] [PDF 0KB] ( 27 )   
doi: 10.1007/s40242-016-5489-8

The self-assembly of a prominent mixed-donor ligand, 5-[4-(1H-tetrazolyl)phen]isophthalic acid(H3TZPI), with a Cd2+ center generates two new metal-organic frameworks:[Cd(H2TZPI)2(H2O)2]n(JUC-163) and[Cd2(TZPI)(μ3-OH)(H2O)2]·H2O·DMF(JUC-164). The two complexes demonstrate different structures for the ligand’s different coordination modes and configurations. JUC-163 shows a 2D layer structure and further forms into a 3D supramolecular framework by noncovalent interactions(C-H…O, O-H…N and ππ interactions), whereas JUC-164 exhibits a fascinating 3D framework for the outstanding coordination modes and configurations of the ligand, which are fit for the complex structure. And also, the factor of different cadmium salts(chloride and nitrate) which are used in synthesis progress is worth to notice for the construction of the two distinct structures. The luminescent properties of these metal-organic frameworks were also investigated.

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ZHANG Qian, WU Xiang, OVSYANNIKOV V. Sergey, DONG Juncai, QIN Shan, DUBROVINSKY S. Leonid, CHEN Dongliang
High-pressure, High-temperature Synthesis and Properties of the Monoclinic Phase of Y2O3
2016 Vol. 32 (4): 545-548 [Abstract] ( 24 ) [HTML 1KB] [PDF 0KB] ( 25 )   
doi: 10.1007/s40242-016-5469-z

The monoclinic phase of Y2O3(B-RES) has been synthesized using a Kawai-type multi-anvil apparatus under 20 GPa at 1800 ℃. Samples of the cubic Y2O3(C-RES) and monoclinic Y2O3 phases were characterized by synchrotron radiation X-ray diffraction, X-ray absorption near edge structure and Raman spectroscopy. Crystal structures of the cubic and monoclinic phases have been examined using Rietveld refinement of the X-ray diffraction data. The cubic-to-monoclinic transition of Y2O3 was reconstructive and irreversible. The X-ray diffraction results were further confirmed by simulation of the X-ray absorption spectra.

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YU Bingwen, JIN Wei, ZHU Dan, YING Yangwei, YU Haixiang, SHAN Jin, XU Chen, LIU Wenlong, JIN Qinhan
Electromagnetic Properties of a New Microwave Plasma Torch with Double Resonance Configuration
2016 Vol. 32 (4): 549-555 [Abstract] ( 23 ) [HTML 1KB] [PDF 0KB] ( 13 )   
doi: 10.1007/s40242-016-6054-1

In order to obtain a stable plasma and improve the performance of the torch for atomic emission spectroscopy(AES), the structure of microwave plasma torch(MPT) was analyzed. The transmission and distribution characteristics of the electromagnetic field of the torch configuration with two or three concentric tubes, as well as the metal spacer between inner and intermediate tubes with different depths were simulated with electromagnetic simulation software and verified by experiments. The results indicate that the inner tube of MPT plays an important role in strengthening the electric field intensity at the opening end of the MPT and redistributing the electromagnetic field in the whole torch by forming a double resonance configuration, and contributes to enhancing the macroscopic stability and the self-sustainment of the plasma. The stability of the plasma is proved to be excellent when the metal spacer between the inner and intermediate tubes is located at a place 20—30 mm away from the top opening of the torch. A proper location of the spacer can also avoid the formation of a static filament plasma or a rotating plasma rooted from the outer wall of the inner tube. With the help of morphological analysis, the underlying reason why MPT possesses a great tolerance to wet aerosols and air introduction was clearly made, that is, the formation region of the plasma formed with MPT is apparently separated from the reaction zone of it.

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SHI Xiaolei, ZHANG Ting, LI Xuwen, FENG Yu, TAN Xin, JIN Yongri
Interaction Between Tangeretin and Ovalbumin to Reduce the Allergic Effects of Ovalbumin
2016 Vol. 32 (4): 556-560 [Abstract] ( 20 ) [HTML 1KB] [PDF 0KB] ( 41 )   
doi: 10.1007/s40242-016-6016-7

Food allergy has become a worldwide problem. To find an effective way to reduce the allergic effect of allergen is an interesting topic. In this work, the interaction between ovalbumin(OVA) and tangeretin was studied by means of spectroscopy, molecular docking calculation and animal experiment. As the results show, static quenching of fluorescence intensity happened due to the interaction between OVA and tangeretin. Binding constants, binding sites, and thermometric parameters were obtained. The conformation changing of OVA occurred due to the interaction between it and tangeretin. The molecular docking calculation results show that the epitopes Arginine 84(ARG84), Leucine 87(LEU87), Asparagine 88(ASN88), Serine 103(SER103), Arginine 104(ARG104), Leucine 124(LEU124), Arginine 126(ARG126), Glycine 127(GLY127), Glycine 128(GLY128) and Tryptohan 148(TRP148) of OVA were occupied by tangeretin after the docking, which means tangeretin may have some inhibition effects. As the results of animal experiments, the amount of IgE and lung tissue sections of female BALB/c mice in different groups show that tangeretin with different concentrations has better effects than dexamethasone. In conclusion, the tangeretin may have the effects to reduce the allergic effects of OVA via occupying the IgE-binding epitopes of OVA.

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WU Min, CUI Long, LING Xiaofeng, XU Zhi
Detection of Cholangiocarcinoma with Fourier Transform Infrared Spectroscopy and Radial Basis Function Neural Network Classification
2016 Vol. 32 (4): 561-564 [Abstract] ( 21 ) [HTML 1KB] [PDF 0KB] ( 34 )   
doi: 10.1007/s40242-016-5470-6

The aim of this study was to explore the possibility of applying Fourier transform infrared(FTIR) spectroscopy as a medical diagnostic tool based on a neural network classifier for detecting and classifying cholangiocarcinoma. A total of 51 cases of bile duct tissues were obtained and later characterized by FTIR spectroscopy prior to pathological diagnosis. The criteria for classification included 30 parameters for each FTIR spectra, including peak position(P), intensity(I) and full width at half-maximum(FWHM), were measured, calculated and subsequently compared against the normal and cancer groups. The FTIR spectra were classified by the radial basis function(RBF) network model. For establishing the RBF, 23 cases were used to train the RBF classifier, and 28 cases were applied to validate the model. Using the RFB model, nine parameters were observed to be pronouncedly different between cancerous and normal tissue, including I1640, I1550, I1460, I1400, I1250, I1120, I1080, I1040 and P1040. In the RBF training classification, the accuracy, sensitivity, and specificity of diagnosis were 82.6%, 80.0%, and 84.6%, respectively. While validating the classification, the accuracy, sensitivity, and specificity of diagnosis were 78.6%, 75.0%, and 81.2%, respectively. The results suggest that FTIR spectroscopy combined with neural network classifier could be applied as a medical diagnostic tool in cholangiocarcinoma diagnosis.

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KANG Meng, ZOU Xue, LU Yan, WANG Hongmei, SHEN Chengyin, JIANG Haihe, CHU Yannan
Application of a Self-developed Proton Transfer Reaction-Mass Spectrometer to On-line Monitoring Trace Volatile Organic Compounds in Ambient Air
2016 Vol. 32 (4): 565-569 [Abstract] ( 15 ) [HTML 1KB] [PDF 0KB] ( 3 )   
doi: 10.1007/s40242-016-5462-6

Real-time and on-line monitoring volatile organic compounds(VOCs) are valuable for real-time evalua- ting air quality and monitoring the key source of pollution. A self-developed proton transfer reaction-mass spectrometer(PTR-MS) was constructed and applied to on-line monitoring trace VOCs in ambient air in Hefei, China. With the help of a self-developed catalytic converter, the background signal of the instrument was detected and the stability of the instrument was evaluated. The relative standard deviation of signal at m/z 21 was only 0.74% and the detection limit of PTR-MS was 97 part per trillion(97×10-12, volume ratio). As a case of the air monitoring in Hefei, the ambient air at Dongpu reservoir spot was on-line monitored for 13 d with our self-developed PTR-MS. Meanwhile, a solid-phase micro-extraction(SPME) technique coupled to gas chromatography-mass spectrometry/mass spectrometry (GC-MS/MS) was also used for the off-line detection of the air. The results show that our self-developed PTR-MS can be used for the on-line and long-term monitoring of VOCs in air at part per trillion level, and the change trend of VOCs concentration monitored with PTR-MS was consistent with that detected with the conventional SPME-GC-MS. This self-developed PTR-MS can fully satisfy the requirements of air quality monitoring and real-time monitoring of the key pollution sources.

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TANG Xiaojian, WANG Jianhui, ZHAO Ke, XUE Honghai, TA Chunhong
A Simple and Rapid Label-free Fluorimetric “Turn Off-on” Sensor for Cadmium Detection Using Glutathione-capped CdS Quantum Dots
2016 Vol. 32 (4): 570-575 [Abstract] ( 35 ) [HTML 1KB] [PDF 0KB] ( 2 )   
doi: 10.1007/s40242-016-5448-4

A convenient label-free fluorescence(FL) nanoprobe for rapid detection of cadmium(Cd) was established using glutathione-capped CdS quantum dots(QDs) and 1,10-phenanthroline(phen). The prepared CdS QDs exhibited a strong FL emission at 536 nm, which could be quenched by phen due to the photoinduced hole transfer(PHT) mechanism. The existence of Cd effectively recovered the FL intensity of CdS QDs, which was due to the easy detachment of phen from the surface of QDs to form[Cd(phen)2(H2O)2]2+ in solution. Cd concentrations were linearly correlated with the FL intensity in the range of 0.0625-1.25 μmol/L under the optimized conditions and the detection limit was 0.01 μmol/L. Finally, the Cd concentration was accurately quantified in real water sample using the proposed sensor.

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LU Haibin, JIN Xiangqun, JIN Yang, HUANG Bangrui, WANG Cheng, WANG Chunhe, MA Fangyuan, CHEN Yuting, LI Jiarui, CONG Yu, WANG Wenlong, SONG Yuming, MU Xupeng
Design, Synthesis, Inhibiting HDACs Ability and Antitumor Activity of Pyrimidin-4(3H)-one Hydroxamate Derivatives
2016 Vol. 32 (4): 576-580 [Abstract] ( 20 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-016-6105-7

A series of novel pyrimidin-4(3H)-one hydroxamate derivatives was designed, synthesized and studied for their activities against histone deacetylases(HDACs). The results indicate that all the compounds show HDACs inhibitiory activity. The antiproliferative activities of the compounds against HeLa and A549 cells were also investigated. The pharmacological results show compound 9g has potent activity in the enzymatic inhibition assay and cell-based assay.

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WANG Yue, HOU Dalong, LÜ Haoze, ZHANG Baozhen, WANG Ensi
Efficient Synthesis of Beraprost Sodium
2016 Vol. 32 (4): 581-585 [Abstract] ( 37 ) [HTML 1KB] [PDF 0KB] ( 37 )   
doi: 10.1007/s40242-016-6093-7

An efficient and straightforward synthesis of beraprost sodium was developed with dicyclopentadiene as a starting material, a one-pot reaction product 5 as key intermediate and the Prins reaction and the Horner-Wads- worth-Emmons reaction as key steps. The structures of the key intermediate and the target compound were confirmed by 1H NMR, 13C NMR and MS. The purity of beraprost sodium identified by high performance liquid chromatography(HPLC) was identical to that of Japanese Pharmacopoeia(16th). This development will be used for the industrial synthesis of beraprost sodium.

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ZHANG Guofu, ZHANG Guihua, LEI Jie, LI Shasha, XU Shengjun, DING Chengrong, SHAN Shang
Aerobic Alcohol Ammoxidation Catalyzed by Copper(I)/Amino Acid: a Scalable Protocol to Nitriles
2016 Vol. 32 (4): 586-593 [Abstract] ( 15 ) [HTML 1KB] [PDF 0KB] ( 3 )   
doi: 10.1007/s40242-016-6067-9

A facile, practical and scalable catalyst system for alcohols ammoxidation into nitriles was developed using amino acid as ligand, oxygen as terminal oxidant and copper iodide(CuI) as catalyst. The catalyst system shows excellent functional groups compatibility for a wide range of testing substrates, even the substrates bearing oxidation- sensitive groups such as MeS-, alkenyl and -NH2 can also work well. In addition, the protocol is readily scaled up to more than 20 g and the product can be obtained just through filtration or distillation without conventional column chromatography.

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GAO Yang, WANG Bowei, GAO Shang, ZHANG Ruhui, YANG Chunying, SUN Zheng, LIU Zhihui
Design and Synthesis of 1,4-Dihydropyridine and Cinnamic Acid Esters and Their Antioxidant Properties
2016 Vol. 32 (4): 594-599 [Abstract] ( 17 ) [HTML 1KB] [PDF 0KB] ( 25 )   
doi: 10.1007/s40242-016-6047-0

In this study, cinnamic acid derivatives with pyridine ring were synthesized via Hantzsch reaction in order to expand conjugation system and their antioxidant abilities were tested. According to the evaluation results of their antioxidant properties, compounds 2 and 3 have similar antioxidant activity to prevent DNA from ·OH- and Cu2+/GSH induced oxidation, demonstrating that 1,4-dihydropyridine and pyridine nucleus exhibit good resistance to oxidation while the substituents have little effect. In the meantime, the AAPH-induced oxidative DNA damage[AAPH=2,2'-azobis(2-methylpropionamidine)dihydrochloride] and trapping ABTS test show that N—H bond and large conjugation systems are the pivotal parts to improve the activities of antioxidant.

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LIU Ming, LIU Yang, ZHOU Sha, ZHANG Xiao, YU Shujing, LI Zhengming
Synthesis and Antifungal Activities of Novel Strobilurin Derivatives Containing Quinolin-2(1H)-one Moiety
2016 Vol. 32 (4): 600-606 [Abstract] ( 33 ) [HTML 1KB] [PDF 0KB] ( 2 )   
doi: 10.1007/s40242-016-6041-6

To discover novel lead compounds with better antifungal activities, a series of novel strobilurin derivatives containing quinolin-2(1H)-one moiety was designed and synthesized via intermediate derivatization method. Their structures were characterized by means of 1H nuclear magnetic resonance(1H NMR), 13C NMR and high resolution mass spectrometry(HRMS). The biological assay results indicate that most target compounds exhibit good to excellent fungicidal activities against 10 plant pathogens. Compounds 4d, 5b and 5c possess 94.1%, 83.8% and 80.9% in vitro inhibition respectively against Rhizotonia cereals at the concentration of 50 μg/mL, which are better than that of the control agents. Especially, the inhibition activities of compound 4d against all of the tested fungi approach or exceed those of the controls. The structure-activity relationship was also discussed.

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ZHANG Dongkai, HUA Xuewen, LIU Ming, WU Changchun, WEI Wei, LIU Yang, CHEN Minggui, ZHOU Sha, LI Yonghong, LI Zhengming
Design, Synthesis and Herbicidal Activity of Novel Sulfonylureas Containing Triazole and Oxadiazole Moieties
2016 Vol. 32 (4): 607-614 [Abstract] ( 35 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-016-6029-2

Three novel series of 5-substituted sulfonylurea derivatives were designed and synthesized via introducing a triazole or oxadiazole ring at the 5th position of the benzene ring in classical sulfonylurea herbicides. All the target compounds were confirmed by means of 1H nuclear magnetic resonance(NMR), 13C NMR and elemental analysis. The bioassay results show that the target compounds containing an oxadiazole ring at the 5th position display moderate to excellent herbicidal activities against Brassica campestris and Amaranthus retroflexus under soil treatment. Especially, compounds zdk20, zdk21 and zdk22 possess 98.6%, 96.5% and 94.5% inhibition rates, respectively, against Amaranthus retroflexus at a concentration of 75 g/ha(1 ha=1×104 m2) under soil treatment, which approach to those of the commercial herbicide chlorsulfuron.

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WANG Caixia, SONG Hailong, LIU Weiqun, XU Cuilian
Design, Synthesis and Antifungal Activity of Novel Thioureas Containing 1,3,4-Thiadiazole and Thioether Skeleton
2016 Vol. 32 (4): 615-620 [Abstract] ( 20 ) [HTML 1KB] [PDF 0KB] ( 5 )   
doi: 10.1007/s40242-016-6023-8

To find new lead compounds with high antifungal activity, a series of new thiourea derivatives containing 1,3,4-thiadiazole and thioether skeleton was designed via linking the active sub-structures. The target compounds were prepared via three steps from the commercially available thiosemicarbazide. Their structures were characterized by means of HRMS, 1H NMR, 13C NMR and IR spectroscopy. The preliminary results indicate that the title compounds show various antifungal activity against the tested fungi. Compounds 4c, 4g, 4h, 4k, 4n, 4o, 4p, 4q and 4r display excellent antifungal activities against one or more tested fungi with inhibitory efficiencies of 90%-100% at 200 μg/mL. Especially, compound 4o shows the best inhibitory effect against Curvularia lunata, Cotton Fusarium Wilt, P. P. var nicotianae and Fusarium spp. with the EC50 values of 28.12, 30.41, 15.2 and 6.22 μg/mL, respectively, which are even superior to those of triadimefon(98.73, 96.58, 105.37 and 102.18 μg/mL). The preliminary structure-activity relationship indicates that allyl and aromatic groups are favorable to their antifungal activities.

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MEN Yican, ZHANG Jiqian, ZHOU Lishan, LI Junqiu, LIU Jun, LI Juan, QU Hongmei
Zirconium-mediated Selective Synthesis of Quinoline Derivatives
2016 Vol. 32 (4): 621-624 [Abstract] ( 24 ) [HTML 1KB] [PDF 0KB] ( 2 )   
doi: 10.1007/s40242-016-6021-x

A series of quinoline derivatives was obtained in high yields by an efficient one-pot reaction of substituted o-diiodobenzenes with azazirconacyclopentadienes, which were conveniently prepared from one internal alkyne and one nitrile mediated by zirconocene. This proposed synthetic method provides a feasible way to the synthesis of large N-heterocyclic π-conjugated molecules.

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KUAN Dingyaw, DU Wei, DAI Lingmei, MA Gaojian, LIU Dehua
Effect of Solvent on the Extraction of Microalgae Lipid for Biodiesel Production
2016 Vol. 32 (4): 625-629 [Abstract] ( 24 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-016-5515-x

The effect of solvent on the microalgae lipid extraction was studied. The efficiency of lipid extraction from microalgae was found to differ according to the solvent used. The existence of formic acid contributed to the extraction of lipid to a great extent. With 8 mg/L formic acid existing in the system, the lipid yield and free fatty methyl ester(FAME) yield increased from 39% to 42% and from 81% to 90% respectively compared to those of the control. The highest lipid yield of 42% was achieved from Chlorella protothecoidesis with an FAME yield of 89% when a mixed solvent of 14 mL/g dichloromethane, 2 mL/g methanol and 4 mL/g formic acid was used.

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ZHU Jian, JIN Zhimin
Efficient Purification of Camptothecin via Aqueous Two-phase System Composed of 1,1,3,3-Tetramethylguanidinium Benzoate Ionic Liquid and K2CO3
2016 Vol. 32 (4): 630-633 [Abstract] ( 39 ) [HTML 1KB] [PDF 0KB] ( 20 )   
doi: 10.1007/s40242-016-5488-9

After being hydrolyzed into corresponding hydrosoluble carboxylate by 1,1,3,3,-tetramethylguanidine (TMG), camptothecin was extracted via the aqueous two-phase systems composed of ionic liquid 1,1,3,3- tetramethylguanidinium(TMGM) carboxylate and K2CO3, and was regenerated at the final by dilute aqueous hydrochloric acid. Among the ionic liquids, TMGM benzoate showed the best effect, TMGM formate the worst, this results were consistent with the liposolubilities of different carboxylic acid components in the ionic liquids. Through two-step extraction of TMGM benzoate ionic liquid/K2CO3 aqueous two-phase under a favorable condition, camptothecin was obtained in a purity of 98.3% and a total yield of 85.1%, from the crude camptothecin extract with a purity of 14.2%.

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MA Xiaoyuan, WU Yi, ZHANG Yanjing, TENG Lesheng, XIE Jing, LIAO Weiwei
Regioselective Synthesis of Functionalized Dihydroquinolines via Organocatalytic Allylic Alkylation
2016 Vol. 32 (4): 634-640 [Abstract] ( 34 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-016-5481-3

The regioselective allylic alkylation of 1,2-dihydroquinolines and Morita-Baylis-Hillman(MBH) adducts has been developed. By surveying various reaction parameters, we summarized the effects of temperatures, relative reactant doses, catalysts, solvents and N-protected groups on the regioselectivity of this transformation. This method provides a facile protocol for the preparation of allylic α-substituted dihydroquinolines.

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HAN Yong, ZHU Lilan, ZHANG Yuyan
Molecular Dynamics Simulation for the Impact of External Electric Fields on CaCl2 Aqueous Solution
2016 Vol. 32 (4): 641-646 [Abstract] ( 64 ) [HTML 1KB] [PDF 0KB] ( 39 )   
doi: 10.1007/s40242-016-6106-6

Non-equilibrium molecular dynamics(MD) simulations were performed according to the electronic anti-fouling technology, and some structural parameters and dynamic parameters of CaCl2 aqueous solution were taken as indicators to compare the different effect on the anti-fouling performance by applying different electric fields. The results show that electric fields can effectively decrease the viscosity of CaCl2 aqueous solution and enhance the ionic activity by enlarging the self-diffusion coefficient. In addition, with the same electric field strength, the electrostatic field is more effective at decreasing the viscosity of CaCl2 aqueous solution and increasing the self-diffusion coefficient of water molecules, while the alternating electric field is more effective at increasing the self-diffusion coefficient of Ca2+. Furthermore, an alternating electric field with different frequencies was applied; the results show that an 800 kHz frequency is most effective to decrease the viscosity, and a 700 kHz frequency is most effective to enhance the self-diffusion coefficient of water molecule. Otherwise, 400 kHz is most effective to enhance the self-diffusion coefficient of Ca2+. Additionally, by studying the change of structure parameters, it was concluded that an external electric field can enhance the hydration between Ca2+ and coordinated water molecules, and the alterna- ting electric field is more effective in this respect.

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REN Hejun, ZHANG Ruonan, WANG Qiaochu, PAN Hongyu, WANG Yan
Garlic Root Biomass as Novel Biosorbents for Malachite Green Removal: Parameter Optimization, Process Kinetics and Toxicity Test
2016 Vol. 32 (4): 647-654 [Abstract] ( 18 ) [HTML 1KB] [PDF 0KB] ( 5 )   
doi: 10.1007/s40242-016-6095-5

The potential of the agricultural waste garlic root to remove malachite green(MG) from aqueous solutions was evaluated. The adsorption of this dye onto garlic root was confirmed by means of Fourier transform infrared analysis(FTIR) and scanning electron microscopy(SEM). The equilibrium data fitted well into the Langmuir mo- del(R2>0.99), and the adsorption kinetics followed the pseudo-second-order equation(R2>0.99). The maximum adsorption capacities of MG onto the adsorbent were 172.41 and 232.56 mg/g with the addition of 1 and 2 g/L garlic root, respectively. The optimal conditions for MG removal were established on the basis of orthogonal experiments(OA16 matrix). The concentrations of both MG and garlic root significantly affected the removal efficiency. The acute toxicity test indicated that the treated MG solutions were less toxic than the parent solutions. These results suggest that garlic root is a potential low-cost adsorbent for removing dye from industrial wastewater.

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ZHAO Yue, HAN Chenhua, HUANG Yuanfeng, QIN Wenli, ZHANG Xiao, KAN Yating, YE Ying
New All-solid-state Carbonate Ion-selective Electrode with Ag2CO3-BaCO3 as Sensitive Films
2016 Vol. 32 (4): 655-660 [Abstract] ( 27 ) [HTML 1KB] [PDF 0KB] ( 26 )   
doi: 10.1007/s40242-016-6062-1

A new all-solid-state carbonate ion-selective electrode was fabricated via electrochemical and ion-exchange reactions with Ag nanoparticles and Ag2CO3-BaCO3 as ion-to-electron transducer and ion-selective layer, respectively. This paper presented the detailed procedures of the construction of the electrode, the applications of the electrode in various experiments, and the corresponding chemical reaction principles involved. The fabricated electrode was characterized by means of scanning electron microscopy(SEM), energy dispersive spectrometer(EDS), and electrochemical analyses. The electrode exhibited stable linear responses to carbonate anions(10-5-10-1 mol/L) with average slope of the curve being -26.56 mV per decade, and showed negligible responses to NO3- , SO42-, and Sal- anions. The electrode was further used to measure the concentration of carbonate anions in boiler water. The measured concentration was lower than that determined via titration. Overall, the electrode exhibited the advantages of miniaturized size, robust construction, and compatibility with other equipment and thus could be ideally integrated into various sensor platforms to collect chemical data from industrial heat exchangers.

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WANG Xinyan, WANG Huan, YANG Xiaotian, SU Xingguang
Photovoltaic Properties of Titanium Dioxide Nanowires with Different Crystal Structures
2016 Vol. 32 (4): 661-664 [Abstract] ( 22 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-016-6036-3

Titanium dioxide(TiO2) nanowires with different crystal structures were successfully synthesized, and their charge transfer properties were further investigated by surface photovoltage(SPV), transient photovoltage(TPV) and surface photocurrent(SPC) techniques. The results reveal that both the surface states and the charge transfer rate of different TiO2 nanowires are highly dependent on their crystal structures.

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KANG Bo, ZHANG Wenli, LIN Haibo, XING Yonghui, ZHAO Jinfeng, WANG Yan
Thermal Transfer During the Activation Process in LiSi/FeS2 Thermal Batteries
2016 Vol. 32 (4): 665-668 [Abstract] ( 38 ) [HTML 1KB] [PDF 0KB] ( 27 )   
doi: 10.1007/s40242-016-6030-9

Thermal batteries(TBs) as primary power sources are widely applied in defense and military affairs, and used in electronic packages and nuclear weapons. The activation time(AT) of TBs restricts the reactive speed of them. Therefore, it is a remarkably important parameter and needs to be studied in detail. In our previous study, the thermal transfer model has already been found during the activation process in TBs. In this work, the experimental TBs were fabricated and tested for validating the model. The error between the average value of test and calculation value from this model is less than 1%. As a result, the thermal transfer function for the activation process in the given TBs[FeS2/LiCl-KCl(MgO)/LiSi containing Fe/KClO4 heat pellet] is suggested.

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ZHAO Baijun, HAN Xu, YANG Fan, DONG Xin, ZHANG Yuantao
Studies on Growth of N-Polar InN Films by Pulsed Metal-organic Vapor Phase Epitaxy
2016 Vol. 32 (4): 669-673 [Abstract] ( 15 ) [HTML 1KB] [PDF 0KB] ( 7 )   
doi: 10.1007/s40242-016-5506-y

We reported the growth of N-polar InN films on N-polar GaN/sapphire substrates by pulsed metal-organic vapor phase epitaxy. The crystalline quality, surface morphology, optical and electrical properties of N-polar InN films were investigated in details by varying the breaking time and trimethylindium(TMIn) duration of pulse cycle. It has been found that when the breaking time and the TMIn duration in each cycle remain at 30 and 60 s, respectively, the N-polar InN film obtained exhibits a better crystalline quality and greater optical properties. Meanwhile, the surface morphology and electrical properties of the N-polar InN films also greatly depend on the given growth conditions.

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WANG Dahui, WEN Hao, CHEN Huaijing, YANG Yujiao, LIANG Hongyan
Chemical Evolution of LiCoO2 and NaHSO4·H2O Mixtures with Different Mixing Ratios During Roasting Process
2016 Vol. 32 (4): 674-677 [Abstract] ( 17 ) [HTML 1KB] [PDF 0KB] ( 24 )   
doi: 10.1007/s40242-016-5490-2

Mixtures of NaHSO4·H2O and LiCoO2 extracted from spent lithium-ion batteries were prepared with molar ratios of 1:1, 1:2 and 1:3. The chemical evolution of the LiCoO2 and NaHSO4·H2O mixtures during the roasting process was investigated by means of thermogravimetric analysis and differential scanning calorimetry (TG-DSC), X-ray diffraction(XRD), scanning electron microscopy(SEM), and X-ray photoelectron spectroscopy (XPS). The results show that the chemical reactions in the LiCoO2 and NaHSO4·H2O mixtures proceed during the roasting process. The Li element in the product of the roasting process is in the form of LiNa(SO4). With the increase of the proportion of NaHSO4·H2O in the mixtures, the Co element evolves as follows: LiCoO2→Co3O4→ Na6Co(SO4)4→Na2Co(SO4)2. The roasting products exhibit dense structures and irregular shapes, and the bonding energy of Co increases.

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JIAO Qingze, WANG Yanfeng, HAO Liang, LI Hansheng, ZHAO Yun
Synthesis of Magnetic Nickel Ferrite Microspheres and Their Microwave Absorbing Properties
2016 Vol. 32 (4): 678-681 [Abstract] ( 22 ) [HTML 1KB] [PDF 0KB] ( 24 )   
doi: 10.1007/s40242-016-5457-3

NiFe2O4 microspheres were synthesized using a solvothermal method. The morphologies and structures of NiFe2O4 micropheres were characterized via a field emission scanning electron microscope(FESEM), a transmission electron microscope(TEM) and an X-ray diffractometer(XRD). The NiFe2O4 microspheres were around 150-200 nm in diameter and assembled by nanoparticles. The magnetic and electromagnetic parameters were measured using a vibrating sample magnetometer and a vector network analyzer, respectively. The obtained products exhibited a saturation magnetization of 60.8 A·m2·kg-1 at room temperature. A minimum reflection loss(RL) of -27.8 dB was observed at 9.2 GHz with a thickness of 3.5 mm, and the effective absorption frequency(RL<-10 dB) ranged from 8.2 GHz to 11.2 GHz, indicating the excellent microwave absorption performance of the NiFe2O4 microspheres in the X-band frequencies.

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SUN Xinyuan, DING Yiming, WEN Xiaoling, OUYANG Jianming
Differences in Adsorption of Anionic Surfactant AOT by Calcium Oxalate: Effect of Crystal Size and Crystalline Phase
2016 Vol. 32 (4): 682-688 [Abstract] ( 43 ) [HTML 1KB] [PDF 0KB] ( 26 )   
doi: 10.1007/s40242-016-5428-8

The adsorption of anionic surfactant sodium diisooctyl sulfosuccinate(AOT) onto calcium oxalate monohydrate(COM) and dihydrate(COD) with sizes of 50, 100 nm, 1, 3 and 10 μm was comparatively studied to simulate the interaction between urinary crystallites and urine components. The adsorption quantity of different concentrations of AOT onto COD and COM with different sizes was detected using a UV-Vis spectrophotometer. The crystalline phase transition of COM and COD before and after adsorption was analyzed by X-ray powder diffraction and Fourier transform infrared spectrometry. The zeta potential of the crystal surface after adsorption of different concentrations of AOT was measured using a zeta potential analyzer. The adsorption quantity of AOT on COM and COD with different sizes was ranked in the following order: 50 nm>100 nm>1 μm>3 μm>10 μm. The adsorption quantity of COM was greater than that of COD with the same size because the density of the positive charges on the COM surface was higher than that on COD surface. With the increase of AOT concentration, the adsorption curves of the large-sized COM and COD(3 and 10 μm) were S-type, whereas the adsorption curves of the small-sized COM and COD(50 nm, 100 nm and 1 μm) were linear. The adsorption capacities of small-sized COM and COD were much greater than those of the 3 and 10 μm crystals. On the basis of the above results, we proposed a molecular model to summarize the absorption of AOT onto COM and COD crystals. Small crystals exhibit a large specific surface area and high surface energy. Thus, the adsorption capacities of them are stronger than those of large crystals. Overall, this study implies that small crystals can easily absorb anionic molecules in urine and may easily adhere to a negatively charged cell surface, thereby increasing the severity of cell injury.

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CHEN Youchun, SUN Yuqian, YU Chengzhuo, LI Fenghong, WANG Yue
Anode Engineering of Highly Efficient Polymer Solar Cells Using Treated ITO
2016 Vol. 32 (4): 689-694 [Abstract] ( 13 ) [HTML 1KB] [PDF 0KB] ( 8 )   
doi: 10.1007/s40242-016-6176-5

ITO substrates were treated with organic solvent cleaning(OSC), SC1 treatment[V(NH4OH):V(H2O2): V(H2O)=1:1:5], O2 plasma and UV ozone, respectively. Combined investigations of atom force microscopy(AFM), water contact angle measurements, ultraviolet photoemission spectroscopy(UPS) and X-ray photoemission spectroscopy(XPS) demonstrated that UV ozone treatment could give rise to the smoothest surface, the most hydrophilic property and the highest work function(WF) of ITO due to the removal of hydrophobic C-O impurity from the ITO surface and the enrichments of more oxygen on the ITO surface. When PEDOT:PSS film[(poly(3,4-ethylenedioxy- thiophene):poly(styrene sulfonate)] was deposited on the ITO substrates treated with UV ozone, it showed a lower root-mean- square roughness in AFM images, a higher transmission in UV-Vis transmission spectra and a higher WF in UPS spectra than the PEDOT:PSS films deposited on the ITO substrates treated by other three methods. As a result, the power conversion efficiency of polymer solar cells(PSCs) based on PTB7:PC71BM as an active layer and ITO treated by UV ozone as an anode can reach 8.48% because of the simultaneously improved short circuit current, open circuit voltage and fill factor compared to the PSCs with ITO treated with other three methods.

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HUANG Hongxiang, HE Wenli, MA Yueyang
Preparation, Characterization, Luminescent and Electrochemical Properties of Ru(bpy)2-functionalized Silica Nanoparticles
2016 Vol. 32 (4): 695-701 [Abstract] ( 17 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-016-6090-x

Ru(II)-complex functionalized silica nanoparticles(nano-SiO2) were prepared via a coordination reaction of cis-dichlorobis(2,2'-bipyridine)ruthenium[Ru(bpy)2Cl2] complex with poly(4-vinylpyridine)(P4VP)-modified nano-SiO2 particles. Both the Ru-complex and the functionalized nano-SiO2P4VP-Ru(bpy) hybrids were doped in poly(methyl methacrylate)(PMMA) to form optically transparent thin films. The composition and spectroscopic properties of the nano-SiO2P4VP-Ru(bpy) hybrids were evaluated with the help of thermogravimetric and elemental analysis, and UV-Vis absorption spectroscopy, infrared spectroscopy, X-ray photoelectron spectroscopy, and fluorescence spectroscopy. Microscopy images revealed that the nanohybrids were approximately 12 nm in diameter and readily formed aggregates following the functionalization with P4VP and Ru(bpy)2Cl2. The as-prepared nano-SiO2P4VP-Ru(bpy) hybrids produced emissions at approximately 604 and 654 nm under radiation both in solution and in doped thin films. Finally, cyclic voltammetry studies on the nanohybrid-modified electrode revealed a redox couple with the cathodic and anodic potentials at approximately 0.28 and 0.73 V(vs. Ag/AgCl), attributed to the one electron transfer of Ru(bpy)22+/3+ immobilized on the nano-SiO2 particles.

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MA Xiaoyu, YANG Jianmao, CAI Wenshu, ZHU Guodong, LIU Jianyun
Preparation of Au Nanoparticles Decorated Polyaniline Nanotube and Its Catalytic Oxidation to Ascorbic Acid
2016 Vol. 32 (4): 702-708 [Abstract] ( 23 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-016-5460-8

With sulfonated electrospun polystyrene fiber as a template, uniform polyaniline(PANI) nanotubes were fabricated via polymerization of aniline followed by template removal. Au nanoparticles(Aunano) were decorated on the PANI nanotube successfully via auto-reduction of HAuCl4 on the PANI nanotube. The morphology of the nanotubes was characterized by means of scanning electron microscopy(SEM) and transmittance electron microscopy(TEM). By varying precursor concentration and incubation time, Aunano-PANI with different size of Aunano was obtained conveniently. Glassy carbon electrode modified with the Aunano decorated PANI nanotubes (Aunano-PANI/GCE) was prepared and used seccessfully for the catalytic oxidation of ascorbic acid(AA). The results of differential pulse voltammetry indicate that there is a good linear relationship between the peak currents and the concentrations of AA in the range of 5-3000 μmol/L, with the limit of detection of 1 μmol/L(S/N>3). There is no mutual interference between AA and dopamine. The electrode has been successfully applied in the detection of AA in vitamin C tablet sample.


Total Cites and Impact Factors of Chinese Chemical Journals of 2013 JCR
The 4th International Symposium on Solar Fuels and Solar Cells (SFSC 2014)
Total Cites and Impact Factors of Chinese Chemical Journals of 2012 JCR
The 14th National Youth Conference on Catalysis

The 8th National Conference on Chemical Biology of China

Cooperation between Editorial Department of “Chemical Research in Chinese Universities” and Springer

The 3th International Conference on Advances in Microfluidics and Nanofluidics (AMN2012)

10th Asian-Pacific International Symposium on Microscale Separations and Analysis(APCE2010)

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