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2017 Vol.33 No.4
 Published: 01 August 2017

Contents | Articles |
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2017 Vol. 33 (4): 0-0 [Abstract] ( 4 ) [HTML 1KB] [PDF 1065KB] ( 10 )   

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WANG Aitian, XU Jun, WANG Chao, DENG Feng, XU Ruren, YAN Wenfu
Structure-directing Effect on Synthesis of Layered Aluminophosphates with Same Topology
2017 Vol. 33 (4): 513-519 [Abstract] ( 16 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-017-7050-9

Three layered aluminophosphates(UiO-15, APDAP12-150 and APDAP-150) with same topology were crystallized from an initial mixture with a molar composition of Al2O3:1.5P2O5:5.5R:227H2O, where R is ethylenediamine, 1,2-diaminopropane or 1,3-diaminopropane, respectively. The crystallization processes of UiO-15, APDAP12-150 and APDAP-150 were investigated using solid-state NMR in combination with XRD and other characterization techniques. The evolution of the coordination states of Al and P in the solid products was monitored, and the possible starting points of crystallization(core units) of UiO-15, APDAP12-150 and APDAP-150 were obtained and analyzed. The formation of a trimer as well as a hexamer of aluminophosphate, a monomer of PO4 and a nonamer containing two three-membered rings is critical for the start of crystallization of UiO-15. The formation of a hexamer and a pentamer is critical for the start of crystallization of APDAP12-150. The formation of an AlO6 monomer and a pentamer containing a three-membered ring is critical for the start of crystallization of APDAP-150. The crystal water played a co-structure-directing role in the formation of APDAP-150.

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JI Yanyan, ZHANG Bing, ZHANG Wu, ZHAO Bo, LI Hongbo, WANG Dongmei, LI Ying
High-efficient Synthesis of Zeolite LTA via a Wet-gel Crystallization Route
2017 Vol. 33 (4): 520-524 [Abstract] ( 15 ) [HTML 1KB] [PDF 0KB] ( 2 )   
doi: 10.1007/s40242-017-7008-y

Zeolite LTA has been largely used as good adsorbent and detergent builder with a huge amount of demand. Numerous efforts have been devoted to the exploration of new synthetic methods for preparing zeolites more conveniently and efficiently. Herein, we reported a wet-gel crystallization route to synthesize zeolite LTA from simple filtration of the initial reaction mixture followed by heating for crystallization. The products were characterized in detail by means of X-ray diffraction, Raman spectra, scanning electron microscopy and elemental analysis. The yields of the solid products were also investigated, which suggested that the wet-gel method afforded an obvious improvement of products yield compared with the conventional synthesis route. For application as detergent builder, the calcium ion exchange rates of the wet-gel synthesized zeolites were similar with that of conventional LTA zeolites. Therefore the wet-gel route would be potentially important in industry due to its advantages of easy-performing, high-yielding and energy-saving.

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YOU Aimei, CAO Yuhua, CAO Guangqun
Facile and Convenient Fabrication of Color-controlled Colloidal Magnetically Assembled Photonic Crystals
2017 Vol. 33 (4): 525-529 [Abstract] ( 49 ) [HTML 1KB] [PDF 0KB] ( 15 )   
doi: 10.1007/s40242-017-6310-z

A facile, convenient and flexible method to tune the structural color of the colloidal magnetically assembled photonic crystals(CMA-PCs) was proposed. The mechanism to tune structural color could be attributed to the significant influence of the surfactant sodium dodecyl sulfate(SDS) concentration on the particle size, especially on the magnetite content of the superparamagnetic composite nanoparticles(MCNPs). By adjusting SDS concentration in miniemulsion polymerization of MCNPs, CMA-PCs with desired diffraction colors could be obtained.

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GUO Ximing, GUO Bin
Preparation of Fe3O4-porphyrin Nano-composited Particles and Their Optical and Magnetic Properties
2017 Vol. 33 (4): 530-533 [Abstract] ( 50 ) [HTML 1KB] [PDF 0KB] ( 2 )   
doi: 10.1007/s40242-017-6261-4

Magnetic Fe3O4 nanoparticles were synthesized via the coprecipitation of ferrous and ferric ion. The morphology and magnetic properties of the magnetic Fe3O4 nanoparticles were investigated by transmission electron microscopy(TEM) and superconducting quantum interference device. Furthermore, the Fe3O4-porphyrin nanocomposite particles(FeOPNCPs) are prepared with Fe3O4 and porphyrin by sol-gel method. The patterns of FeOPNCPs were also characterized by means of scanning electron microscopy(SEM) and TEM. The optical and magnetic properties of FeOPNCPs were investigated on a UV-Vis spectrophotometer, a fluorescence spectrophotometer and a superconducting quantum interference device. These experimental results show that FeOPNCPs not only possess optical features of porphyrin but also retain the superparamagnetic features of Fe3O4 nanoparticles.

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FENG Yusha, BAI Lifei, WANG Shaodan, KONG Xiangyi, CONG Lele, ZHAO Qing, YANG Qingbiao, LI Yaoxian
A Novel Ratiometric Fluorescent Probe for Cyanide Anion with High Selectivity and Its Application in Cell Imaging
2017 Vol. 33 (4): 534-539 [Abstract] ( 16 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-017-7036-7

A novel hybrid acenaphthene-hemicyanine dye(Acc) was designed and synthesized as a colorimetric and ratiometric fluorescent sensor for cyanide detection. The nucleophilic addition of cyanide anion resulted in the blocking of the intramolecular charge transfer(ICT). Thus, the sensor exhibited high sensitivity and selectivity t owards cyanide anion among many anions in dimethylsulphoxide(DMSO)-water media, with the emission wavelength displaying a very large shift(186 nm). Moreover, the color changes of the solution could be observed by the naked eyes and it had a short response time. Under optimized conditions, the detection limit for cyanide was calculated to be 1.3 μmol/L(R2=0.9958). In addition, the probe had excellent biocompatibility and could be utilized to monitor cyanide in living cells.

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WANG Jiangning, SU Ping, LI Di, WANG Ting, YANG Yi
Fabrication of CeO2/rGO Nanocomposites with Oxidase-like Activity and Their Application in Colorimetric Sensing of Ascorbic Acid
2017 Vol. 33 (4): 540-545 [Abstract] ( 3 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-017-7002-4

Nanomaterial-based artificial enzymes(nanozymes) have shown great potential for application in colorimetric sensing. In this paper, the nanocomposites of CeO2 and reduced graphene oxide(rGO) were fabricated via a one-pot hydrothermal process, in which CeO2 nanoparticles were well anchored on the surface of rGO. The prepared CeO2/rGO nanocomposites exhibited excellent catalytic activity for the oxidation of 3,3',5,5'-tetramethylbenzidine(TMB) in the presence of O2. Compared with the individual CeO2 nanoparticles, the nanocomposites had a higher affinity and adsorptivity towards the substrate TMB, which was due to the combination of rGO. In addition, based on the oxidase-like activity of CeO2/rGO nanocomposites, a facile and sensitive colormetric sensor for ascorbic acid(AA) was investigated. The detection limit of AA was low(0.15 μmol/L) and the linear detection range was between 0.5 μmol/L and 40 μmol/L. Furthermore, the colorimetric system was used for the detection of AA in medicine and food analysis, such as tablets, beverage and milk powder.

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TIAN Xiao, YANG Meiqi, GUO Sen, LIU Qingchao, ZHANG Li, HO Chi-Tang, BAI Naisheng
Quantitative Analysis and Chemical Fingerprint Similarity for Quality Control of the Seeds of Paeonia suffruticosa Andr. by HPLC
2017 Vol. 33 (4): 546-551 [Abstract] ( 13 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-017-6463-9

According to the General Office of the State Council of China, tree peony seeds(TPSs, Paeonia suffruticosa Andr.) are considered an emerging source for edible oil. In Chinese folk medicine, TPSs are used for alleviating waist and leg pain. In the present study, a simple, accurate and rapid fingerprint method based on high performance liquid chromatography with diode array detection(HPLC-DAD) was developed and validated to quantify the profiles of ten representative compounds in TPSs. All standard calibration curves exhibited good linearity(R2>0.9995) in the HPLC-DAD analysis. The recovery of the standards ranged from 96.37% to 102.10%. The results show that stilbenoids are the major constituents in TPSs, and their total content ranges from 25.71 mg/g to 54.03 mg/g. Suffruticosol A, suffruticosol B, trans-ε-viniferin, ampelopsin E and paeoniflorin are the major components in methanolwater(80:20, volume ratio) extracts with average contents of 3.962, 12.264, 5.826, 14.060 and 12.755 mg/g, respectively. Additionally, 14 batches of seeds collected from different regions were used to establish a reference fingerprint. Their similarity values were higher than 0.944 except for the sample(0.863) from Linxia. These results collectively indicate that the quantitative HPLC fingerprint method can serve as a prerequisite quality control for TPSs, and is a promising resource for developing new herbal or food products.

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BIAN Min, TIAN Ling, YAO Cheng
An Improved Method of Simultaneous Determination of Four Bioactive Compounds in Evodiae Fructus Using Ionic Liquids as Mobile Phase Additives in High Performance Liquid Chromatography
2017 Vol. 33 (4): 552-558 [Abstract] ( 5 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-017-6434-1

There are many compounds with different structures and chemical properties in Evodiae Fructus. It is hard to simultaneously determine the bioactive compounds by high performance liquid chromatography(HPLC). A new method was proposed for four bioactive compounds(synephrine, limonoids, evodiamine and rutecarpine) to be separated completely and determined accurately using ionic liquids(ILs) as mobile phase additives. The mechanism and the effect of the ILs for changing the chromatographic behaviors of the four compounds were studied by systematically changing the pH value of mobile phase, the types and concentrations of ILs as well as the concentrations of phosphate buffer. The chromatographic behaviors of the analytes with a mobile phase containing ILs complied with the stoichiometric displacement model for retention(SDM-R). All results demonstrate the dual nature of ionic liquids, which are competitive adsorption and ion-pair agent. Meanwhile, excellent linearity was observed for all the compounds with correlation coefficients between 0.9992 and 0.9998. The limit of detection and the limit of quantification of the four compounds varied from 0.47 μg/mL to 0.87 μg/mL and from 1.79 μg/mL to 2.44 μg/mL, respectively. Three kinds of Evodiae Fructus processed through different methods were analyzed via the method. The result shows that the contents of evodiamine and rutecarpine as the two main active compounds by processing with vinegar and salt are obviously higher than those of the raw products.

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YANG Jiajia, WANG Meng, LI Xia, FAN Ningning, XUE Liangmin, LI Hao, TIAN Chao, WANG Xiaowei, LIU Junyi, ZHANG Zhili
Syntheses and Antiproliferative Evaluation of 6-Thienyl, 6-Polyphenyl Aryl and 6-Naphthyl Derivatives of 2,4-Diaminopyrido[3,2-d]pyramidine as Non-classical Antifolate Targeting DHFR
2017 Vol. 33 (4): 559-568 [Abstract] ( 4 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-017-7153-3

A series of 6-thienylethenyl, 6-polyphenyl arylethenyl, 6-thienylethyl and 6-polyphenyl arylethyl derivatives of 2,4-diaminopyrido[3,2-d]pyrimidine for targeting dihydrofolate reductase(DHFR) was designed and synthesized as non-classical antifolates in order to overcome drug resistance. The compounds were evaluated for in vitro antitumor activities, rhDHFR and antimicrobial activities. All the compounds exhibited antitumor activities, with values in the range of 0.13-17.8 μmol/L against HL-60, HeLa and A549. Both the types of aryl groups and the orientation of polyphenyl aryl made an impact on the biological activities. 6-Naphthylethyl derivatives 5c and 5d were proved to be the most active DHFR inhibitors, which were more potent than 6-phenylethyl, 6-thienylethyl and 6-biphenylethyl derivatives. Docking studies reveal that flexible saturated carbon-carbon bond of C9-C10 is essential for biological activities in molecular backbone. Antimicrobial test shows that most of the compounds exhibit antibacterial activities.

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WANG Bowei, HOU Wanshi, WANG Yingnan, LI Shaoheng, LIU Zhihui, SONG Zhiguang
Synthesis and Pharmacodynamics of Ibuprofen-1-acetoxyethyl Ester
2017 Vol. 33 (4): 569-573 [Abstract] ( 9 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-017-7103-0

Ibuprofen(IBU) and its derivatives are widely used in treating many diseases, such as depression, glomerulonephritis, fever caused by common cold or influenza, and rheumatoid arthritis. While in clinical trials, IBU was found to have many side effects. To weaken and prevent these side effects, a derivative called ibupr ofen-1-acetoxyethyl ester was synthesized in this paper. The maximum concentration(cmax) in a shorter time was compared with IBU at the same dose.

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ZHAO Wenkai, WANG Zhiming, LI Xueying, ZHANG Dongdong, ZHANG Xiaojuan, LU Ping
Preparation of 9,10-Diarylphenanthrene Derivative and Its Application in Full Color Emitters Synthesis
2017 Vol. 33 (4): 574-580 [Abstract] ( 8 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-017-7044-7

As a building block with high photo-and thermo-stability, phenanthrene plays an important role in the preparation of blue(or deep-blue) and full color fluorescence materials. However, some critical issues must be addressed before its full potential can be realised, such as its tedious and low-yield modification processes and the red-shift effect in its aggregated state. In this work, the inexpensive raw material 9,10-phenanthrenequinone(PQ) was chosen as the preparatory functional phenanthrene block. After modifying PQ via halo-substituted, nucleophilic and rearrangement reactions with high yields, the corresponding monomers featured high reactivity and solubility. Compared with classical synthetic approaches for similar phenanthrene-based derivatives, the low efficiency ring-closed reaction and hazardous lithium-injection operation can be omitted using this approach. This new building block demonstrates a clear steric effect following the introduction of peripheral phenyl and alkoxy groups; moreover, stacking in the aggregated state is avoided, which benefits controlling the bandgap and maintaining blue emission as either an emitter or a donor. By changing the central building block in three oligomers, emission of the three primary colors was achieved in solution and film via the conjugated increment and charge-transform effect. This work provides a method of modifying phenanthrene by a simple and efficient synthesis route with inhibition of solid-state aggregation and offers an effective strategy to further develop functional phenanthrene-based building blocks.

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GUO Jinhua, TAN Bei, YE Qingmei, LIANG Guangping, YI Min, JIANG Renwang
Synthesis and Cytotoxic Activities of Spin-labeled Derivatives of Cinobufagin
2017 Vol. 33 (4): 581-586 [Abstract] ( 23 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-017-7025-x

Two series of novel spin-labeled derivatives of Cinobufagin(compounds 5 and 8a-8f in series 1 with five-membered ring nitroxyl free radical and compounds 6 and 9a-9f in series 2 with six-membered ring nitroxyl free radical) were synthesized. The cytotoxic activities in vitro against two tumor cell lines(HepG2 and HeLa) were evaluated, and the results indicate that all compounds display potent cytotoxicity against HepG2 and HeLa cells, and most compounds show better activities on HeLa cells than on HepG2 cells except for compounds 8a and 9d. Generally, the compounds in series 2 have more potent cytotoxic activity against HepG2 than the compounds in series 1. Especially, compounds 6 and 9f in series 2 exhibit even more potent activities against the two tumor cell lines than Cinobufagin. Thus incorporation of different L-amino acids as the linker changed the cytotoxic profile of the spin-labeled Cinobufagin. In addition, the representative compound 9f significantly changed the cell cycle distribution and led to HeLa cell cycle arrested at G2/M phase.

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TIAN He, LIU Yuqiang, LI Xingwei, XIE Yafei, LIU Changying, WANG Jianwu, ZHAO Guilong
A Facile Synthetic Approach to 3-Halo-4-substituted-1,5-dihydro-4H-1,2,4-triazoline-5-thiones Based on Retro-Michael Addition
2017 Vol. 33 (4): 587-593 [Abstract] ( 27 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-017-7044-5

A facile 3-step synthetic approach to 3-halo-4-substituted-1,5-dihydro-4H-1,2,4-triazoline-5-thiones (1a-1k) from corresponding unhalogenated 8a-8i was developed based on the strategy of retro-Michael addition, with the key steps being regioselective S-alkylation of compounds 8a-8i with ethyl 3-iodopropionate(12c) and alkaline cleavage of the propionate protecting group via retro-Michael addition. The synthetic approach was characterized by simplicity of operation and wide substrate scope.

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SHI Ling, ZHANG Yanhua, WANG Caifang, LIU Haoran, WANG Qiuan
Synthesis and Acetylcholinesterase Inhibitory Activity of Polymethoxyflavone Mannich Base Derivatives
2017 Vol. 33 (4): 594-597 [Abstract] ( 2 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-017-6462-x

A series of novel polymethoxyflavone Mannich base derivatives 1-8 was synthesized by Mannich reaction of 5-hydroxy-3,7,3',4'-tetramethoxyflavone 9 with various secondary aliphatic amines and formaldehyde. Their acetylcholinesterase(AChE) inhibitory activities were evaluated. The results showed that most of them exhibited AChE inhibitory activity and especially piperidin-1-yl methyl substituent derivative 5(IC50=0.238 μmol/L) demonstrated stronger activity comparable with the positive control, neoeserinemethyl sulfate(IC50=1.39 μmol/L), which is worthy of further development as an agent for Alzheimer's disease treatment.

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WANG Tongtong, SONG Yinqing, WANG Min, TANG Xiaoyan, ZHOU Jian, YANG Mengrui
Total Synthesis and High Performance Liquid Chromatography Analysis of Phenylethanolamine A
2017 Vol. 33 (4): 598-602 [Abstract] ( 33 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-017-6451-0

A simple, effective and reliable synthetic method was developed to construct beta-agon phenylethanolamine A(PEAA) in good yield with 4-nitrobenzyl bromide as the starting material, which underwent SN2 reaction with ethyl acetoacetate, followed by hydrolysis with concentrated HCl and amination by Leukart reaction to furnish 4-(4-nitrophenyl)butan-2-amine(A). A one-pot reaction was studied to construct PEAA skeleton and reduced carbonyl with KBH4, the conditions were optimized, including reaction temperature, reaction time, solvent and the molar ratio of 2-bromo-1-(4-methoxyphenyl)ethanone(B) to A. Meanwhile, a reliable and practical high performance liquid chromography(HPLC) method with UV detector was developed after screening wavelength, chromatographic column and optimization of mobile phase. The optimal conditions of detecting PEAA were water(0.1% formic acid and 0.1% triethylamine)-methanol(volume ratio 44:56) at 278 nm with plus-C18 column. The above synthetic method would be used to synthesize standard reference materials and advance extensive application of analytical method. In order to ensure food safety and safeguard human health, the analytical method might be used as a standard method in detection and supervision of PEAA.

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ZHANG Wan, WANG Qi, FENG Xing, YANG Li, WU Youke, WEI Xianfu
Anthracene-based Derivatives:Synthesis, Photophysical Properties and Electrochemical Properties
2017 Vol. 33 (4): 603-610 [Abstract] ( 20 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-017-6431-4

A series of anthracene-based derivatives, namely, 9-(4-phenyl)anthracene(1), 9-(4-phenylethynyl)-anthracene(2) and 9, 10-bis(phenylethynyl)anthracene(3), was synthesized by the Suzuki/Sonogashira cross-coupling reactions in good yields. These compounds were fully characterized by X-ray crystallography, thermogravimetric analysis(TGA), differential scanning calorimetry(DSC), UV-Vis absorption and fluorescence(FL) spectroscopy, as well as density functional theory(DFT) calculations. Single-crystal X-ray analysis revealed that the packing structures were influenced by the terminal substitutions. All the compounds exhibited high thermal stability(Td=221-484℃) and blue emission with a high quantum yield(Φf=0.20-0.75). As the number of substituents increased, the decomposition temperatures(Td) of these compounds increased in the following order:1 < 2 < 3. Experiments on the photophysical properties revealed that different substituents strongly affected the optical properties. In particular, compound 1b with the electron-withdrawing group(-CHO) exhibited a larger Stokes shift(113 nm) than the other compounds. Investigation of the electrochemical properties of these compounds showed that the HOMO-LUMO energy gaps(Egap) decreased obviously as the degree of conjugation increased.

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ZHANG Lei, ZHOU Fan, ZHANG Laitao, PENG Lizhi, GUO Cuiping, LUO Cheng, CHEN Heru
Incorporation of Dihydroartemisinin into Memantine Through a Propriate Spacer to Make Hybrid with Enhanced Effects to Protect PC12 Cells from Corticosterone-caused Impairments
2017 Vol. 33 (4): 611-622 [Abstract] ( 16 ) [HTML 1KB] [PDF 0KB] ( 2 )   
doi: 10.1007/s40242-017-7055-4

Ten memantine(Mema)-dihydroartemisinin(DHA) ligands were designed and synthesized. Three types of isomers including α,β, and a defined γ isomer were found in each intermediates(1a-1e). Type γ isomer was firstly reported here and confirmed as a less stable eclipsed conformation. The bonding of Mema with DHA through different carbon chains generally makes the new entities more cytotoxic than either Mema or artemisinin(Arte). The β Mema/DHA ligands are a little bit more cytotoxic than α ligands. By applying corticosterone(Cort)-impaired PC12 cells models, it was found that Mema and those ligands with more than 3 carbon chains showed weak or no neur oprotective activities against the insults. However, two ligands, 2a(β) and 2b(β) showed better effects than either Arte or their combination(Mema/Arte in 1:1 molar ratio) at a dose of 5 μmol/L. Furthermore, ligands 2a(β), 2b(β) and 2c(β) were confirmed as mild N-methyl-D-aspartate(NMDA) antagonists, and their corresponding α isomers are weak NMDA antagonists. All the data indicate that the bonding of Mema/DHA in compacted β conformation mode results in enhanced effects against Cort-induced insults in PC12 cells and might reverse memantine as an anti-depression NMDA antagonist.

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LIU Yanli, CHEN Long, CHEN Dongping, WANG Weina, LIU Fengyi, WANG Wenliang
Computational Study on Mechanisms of C2H5O2+OH Reaction and Properties of C2H5O3H Complex
2017 Vol. 33 (4): 623-630 [Abstract] ( 10 ) [HTML 1KB] [PDF 0KB] ( 2 )   
doi: 10.1007/s40242-017-7055-4

A comprehensive theoretical study on the bimolecular reaction of C2H5O2 with OH radicals was performed at the CCSD(T)/6-311++G(2df,2p)//B3LYP/6-311+G(d,p) level of theory. The calculation results show that C2H5O2 + OH reaction proceeds on both the singlet and the triplet potential energy surfaces(PESs). On the singlet PES, the favorable pathway is the addition of OH radical to the terminal oxygen atom of C2H5O2 radical, leading to the formation of trioxide C2H5O3H with a barrierless process. Then, the trioxide directly decomposes to the products C2H5O and HO2 radicals. On the triplet PES, the predominant pathways are α and β hydrogen atom abstractions of C2H5O2 radical by OH radical-forming products 3CH3CHO2+H2O and 3CH2CH2O2, and the corresponding barriers are 12.02(3TS8) and 19.19 kJ/mol(3TS9), respectively. In addition, the comprehensive properties of trioxide C2H5O3H were investigated for the first time. The results indicate that the trioxide complex RC1 can exist stably in the atmosphere owing to a significantly large and negative enthalpy of formation(-118.44 kJ/mol) as well as a high first excitation energy(5.94 eV).

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YI Tingting, ZHENG Bing, YU Haitao, XIE Ying
Structures, Stabilities and Work Functions of Alkali-metal-adsorbed Boron α1-Sheets
2017 Vol. 33 (4): 631-637 [Abstract] ( 10 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-017-7038-5

In this study, we employed the density functional theory method to simulate Li-, Na-and K-adsorbed boron α1-sheets(α1-BSTs). After optimizing possible structures, we investigated their thermodynamic stabilities, barriers for metal atom diffusion on the substrate, and work functions. The computed results indicate that the work function of α1-BST decreases significantly after the adsorption of Li, Na and K. Furthermore, under high hole coverage, these alkali-metal-adsorbed α1-BSTs have lower work functions than the two-dimensional materials of greatest concern and the commonly used electrode materials Ca and Mg. Therefore, the Li-, Na-and K-adsorbed α1-BSTs are potential low-work-function nanomaterials.

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WANG Hongzhi, SHI Xin, SHI Yulei, ZHANG Weiguo, YAO Suwei
One-pot Hydrothermal Synthesis of Novel NiCoO2/Reduced Graphene Oxide Composites for Supercapacitors
2017 Vol. 33 (4): 638-642 [Abstract] ( 13 ) [HTML 1KB] [PDF 0KB] ( 2 )   
doi: 10.1007/s40242-017-7026-9

Novel NiCoO2/rGO composites with a structure of NiCoO2 nanoparticles anchored on layers of reduced graphene oxide(rGO) were synthesized via a simple one-pot hydrothermal method and were used as faradaic electrodes for supercapacitors. The microstructures of NiCoO2/rGO composites were characterized by means of field emission scanning electron microscopy(FESEM), transmission electron microscopy(TEM), X-ray diffraction(XRD) and thermogravimetric analysis(TGA). When acting as faradaic electrodes for supercapacitors, NiCoO2/rGO composites exhibited a specific capacity of 288 C/g at the current density of 2 A/g and maintained 139.98 C/g at 20 A/g. High capacity retention ratios up to 88% could be achieved after 1000 cycles at a current density of 2 A/g. The outstanding cycling stability was primarily attributed to the combination of mixed transition metal oxides and rGO, which not only maintains a high electrical conductivity for the overall electrode but also prevents the aggregation and volume expansion of electrochemical materials during the cycling processes.

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CHENG Kai, YANG Wei, WANG Hui, ZHOU Jie, WU Shengji, YU Tianming, PAN Jianbo
Effect of Cu(Ⅱ) on Degradation and Decolorization of Rhodamine B in Subcritical Water
2017 Vol. 33 (4): 643-647 [Abstract] ( 14 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-017-6501-7

In this paper, subcritical water, an environmentally friendly solvent, was employed to degrade rhodamine B, which served as a model dye in textile industrial effluents. The effect of Cu(Ⅱ) on the degradation of rhodamine B was evaluated. Further, the degradation kinetics of rhodamine B in subcritical water was evaluated via a Weibull model. The results show that subcritical water could efficiently degrade and decolorize rhodamine B. The addition of Cu(Ⅱ) into subcritical water could accelerate the degradation of rhodamine B and lower the temperature for its complete degradation. The Weibull equation could well express the degradation kinetics of rhodamine B. The calculated rate constants showed Arrhenius behavior and presented high correlation coefficients. The activation energy was 109.4 kJ/mol for subcritical water degradation of rhodamine B, whereas it became lower(93.4 kJ/mol) when Cu(Ⅱ) was added to the subcritical water. The frequency factors for the degradation of rhodamine B by subcritical water without and with Cu(Ⅱ) were calculated to be 1.0×1011 and 3.2×109 min-1, respectively. The above results indicate that subcritical water treatment is a promising process for degrading and decolorizing textile dyes. The results will provide a theoretic support for the industrial application of subcritical water treatment.

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ZHENG Kai, DI Mingyu, ZHANG Jubo, BAO Wenhui, LIANG Daxin, PANG Guangsheng, FANG Zhenxing, LI Chunyuan
Solvothermal Synthesis of Magnetic Fe3O4 Nanospheres and Their Efficiency in Photo-Fenton Degradation of Xylenol Orange
2017 Vol. 33 (4): 648-654 [Abstract] ( 20 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-017-6493-3

Magnetic Fe3O4 nanospheres with a average diameter of (201±0.5) nm were synthesized at 200℃ via a solvothermal method. The as-synthesized Fe3O4 nanospheres performed an efficiency in the Fenton degradation of xylenol orange with a degradation rate of 90%-95%. Additionally, the catalyst was easily recyclable and the recovery rate was greater than 90%. Moreover, the catalyst could be regenerated under an ultrasonic treatment, and the degradation performance remained essentially the same. More importantly, the degradation rate varied with respect to the amount of H2O2 and the pH of the best reaction process. And the reaction efficiency was achieved with 1.5 mL of H2O2 in an acidic environment.

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MENG Lingzong, GUO Yafei, LI Dan, DENG Tianlong
Solid and Liquid Metastable Phase Equilibria in the Aqueous Quaternary System Li+, Mg2+//SO42-, Borate-H2O at 273.15 K
2017 Vol. 33 (4): 655-659 [Abstract] ( 39 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-017-6404-7

The metastable phase equilibria of the Li+, Mg2+//SO42-, borate-H2O system at 273.15 K were studied using isothermal evaporation method. The dry-salt phase diagram, water-phase diagram and the physicochemical property diagrams of the system were plotted with the metastable solubility values and physicochemical properties corresponding to density, refractive index, pH value and conductivity. The dry-salt diagram was composed of four crystallizing zones[lithium sulfate hydrate(Li2SO4·H2O), epsomite(MgSO4·7H2O), lithium metaborate octahydrate(LiBO2·8H2O), and hungchaoite(MgB4O7·9H2O)], five univariant curves and two invariant points (Li2SO4·H2O+MgSO4·7H2O+MgB4O7·9H2O and Li2SO4·H2O+LiBO2·8H2O+MgB4O7·9H2O). Li2B4O7 converted into LiBO2 in solution. Comparing the metastable phase diagram at 273.15 K and stable phase diagram at 298.15 K for the system, the crystallized area of Li2SO4·H2O and MgSO4·7H2O became large, whereas, the other phase regions became small. The J(H2O) changes regularly with increasing J(SO42-), and the physicochemical properties change regularly with the concentration of B4O72- increasing.

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MA Jun, LAN Yang, MAO Hui, LIAO Yang, ZHAO Shilin
Preparation of Pt/γ-Al2O3-C Heterogeneous Catalyst for Highly Selective Hydrogenation of Cinnamaldehyde Towards Cinnamyl Alcohol
2017 Vol. 33 (4): 660-665 [Abstract] ( 21 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-017-6345-1

A Pt/γ-Al2O3-C heterogeneous catalyst with improved catalytic performance was successfully prepared. Bayberry tannin(BT), an abundant natural plant polyphenol, was utilized to modifiy the surface of the γ-Al2O3 matrix and then stabilize Pt nanoparticles(NPs). The catalyst was systematically and specifically characterized by a collection of analytic tools including XRD, XPS, FTIR, TEM, and TG. It was found that the Pt NPs were envenly dispered on the γ-Al2O3-C matrix. Meanwhile, when the catalyst was applied for selective hydrogenation of cinnamaldehyde(CMA) in the presence of KOH promoter in solvent, excellent catalytic performance was obtained. The selectivity to cinnamyl alcohol(CMO) reached 97.88% with 88.45% CMA conversion within 30 min in the presence of 0.037 mol/L KOH, without significant loss of catalytic activity even under cyclic measurements for 5 times. The excellent catalytic performances should be ascribed predominantly to the uniform and stable dispersion of Pt NPs on the γ-Al2O3-C matrix and the excellent heat stability of BT.

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TANG Qiuping, JIANG Wei, HU Gengshen
Effect of Amine Structure on CO2 Capture Performance of Amine-modified SBA-15
2017 Vol. 33 (4): 666-671 [Abstract] ( 23 ) [HTML 1KB] [PDF 0KB] ( 0 )   
doi: 10.1007/s40242-017-6340-6

To investigate the relative CO2 capture performance of "molecular basket" type solid amine sorbents with varying amine structural characteristics, two model amine isomers, triethylenetetramine(TETA) and tris(2-aminoethyl)-amine(TAEA), were chosen alongside mesoporous silica SBA-15 as a support. The CO2 capture performance of each amine derivative was evaluated using a breakthrough method with a fixed-bed reactor. The results show that, in the absence of moisture, the SBA-TETA sorbents show better CO2 capture performance than the SBA-TAEA sorbents; on the other hand, in the presence of moisture, the SBA-TAEA sorbents show slightly improved uptake compared to the SBA-TETA sorbents. The tertiary amine groups, such as those found on TAEA, are known to be un-reactive with CO2 in the absence of moisture, but is activated in the presence of moisture may account for these findings.

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Effect of Reduction and Carburization Pretreatment on Iron Catalyst for Synthesis of Light Olefins from CO Hydrogenation
2017 Vol. 33 (4): 672-677 [Abstract] ( 41 ) [HTML 1KB] [PDF 0KB] ( 7 )   
doi: 10.1007/s40242-017-6316-6

Effect of reduction and carburization pretreatment on iron catalyst for CO hydrogenation to light olefins was investigated. The bulk structure and surface composition of the catalysts during pretreatment were characterized by means of X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS) and high-resolution transmission electron microscopy(HRTEM). The results indicated that phase transformation of iron phases involved α-Fe2O3→Fe3O4α-Fe both in the bulk and on the surface layers in hydrogen atmosphere. However, α-Fe2O3 was firstly transformed to Fe3C and then to Fe5C2 in CO atmosphere, while in syngas atmosphere directly to Fe5C2. As carburization pretreatment time was prolonged, the degree of carburization on the surface increased, and the increase degree of iron catalyst carburization in CO pretreatment was stronger than that in syngas pretreatment. It inferred that surface carbon species was more easily formed in syngas pretreatment instead of iron carbide in CO pretreatment. After hydrogen pretreatment, when the catalyst was reduced to a mixture of magnetite and metallic iron, the selectivity to light olefins was relatively low. Under the joint effects of the active sites from surface iron carbide and surface carbon layers blocking the active sites, longer CO pretreatment time resulted in higher methane selectivity and less light olefins. The selectivity to methane on H2-pretreated catalyst was lower than that of CO-pretreated catalyst.

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GAO Shenghan, GAO Ruichang
Antibacterial Cellulose Composite Membranes Prepared in Ionic Liquid via Phase Inversion Method
2017 Vol. 33 (4): 678-683 [Abstract] ( 15 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-017-6423-4

Antibacterial cellulose/TiO2 nanoparticles(CTM), cellulose/ZnO nanoparticles(CZM) and cellulose/chitosan(CCM) composite membranes were successfully prepared using ionic liquid(IL), 1-butyl-3-methylimidazolium chloride([BMIM]Cl), via phase inversion while[BMIM]Cl was recycled through evaporation and used to prepare cellulose membrane(CM-RILs). The pure water flux(PWF) was significantly increased via adding TiO2, ZnO and chitosan to cellulose and a perfect retention value of 67000 bovine serum albumin(BSA) was achieved in all the prepared membranes. The bacterial reduction of cellulose/TiO2 membrane, cellulose/ZnO membrane and cellulose/chitosan membrane with a blend ratio of 10:3[m(cellulose):m(additive)] was the maximum and reached 100%, 100% and 97.2% for S. aureus and 100%, 99.8% and 97.0% for E. coli, respectively. The results demonstrate that cellulose/TiO2 membrane, cellulose/ZnO membrane and cellulose/chitosan membrane can act as good antibacterial materials in water treatment, medical treatment, food industry as well as other applications.

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HUANG Hailiang, ZU Xihong, YI Guobin, ZHONG Benbin, LUO Hongsheng
Nanopattern Transformation of ABC Triblock Copolymer Thin Films Induced by Strong Solvent Selectivity and Annealing
2017 Vol. 33 (4): 684-688 [Abstract] ( 15 ) [HTML 1KB] [PDF 0KB] ( 1 )   
doi: 10.1007/s40242-017-6381-x

Nanopattern transformation behaviors of polyisoprene-block-polystyrene-block-poly(2-vinylpyridine) (PI-b-PS-b-P2VP) asymmetric ABC triblock copolymer were investigated systematically with various control parameters, including different solvents for polymer solution and annealing conditions in this paper. Ordered nanopattern of PI-b-PS-b-P2VP with hexagonal cylinders could be obtained when PI-b-PS-b-P2VP toluene solution was spin-coated on silicon substrate followed by toluene vapor annealing process. When the film with hexagonal and cylindrical nanopattern was exposed to saturated toluene vapor, the order-order transition of cylindrical nanopattern to parallel nanopattern was observed due to the strong selectivity of toluene to PS and PI blocks. Furthermore, fingerprint nanopattern could also be obtained by solvent annealing in tetrahydrofuran vapor. The nanopattern transformation was due to different selectivity of solvents and incompatibilities of the three blocks of PI-b-PS-b-P2VP under various solvent annealing conditions.


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