CHEMICAL RESEARCH IN CHINESE UNIVERSITIES
 
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2018 Vol.34 No.1
 Published: 01 February 2018

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2018 Vol. 34 (1): 0-0 [Abstract] ( 1 ) [HTML 1KB] [PDF 3864KB] ( 7 )   
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Articles
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ZHANG Jiaqi, WANG Shan, YUAN Long, HOU Changmin
Hydrothermal Synthesis and Magnetic Properties ofSmCr0.5M0.5O3(M=Fe and Mn) Micro-plates
2018 Vol. 34 (1): 1-7 [Abstract] ( 1 ) [HTML 1KB] [PDF 0KB] ( 6 )   
doi: 10.1007/s40242-017-7334-0

Nanostructured B-site Fe and Mn doped SmCrO3 was prepared by mild hydrothermal growth. The as-prepared crystals are mainly micrometer-scale plates, ranging from rhombus(SmCr0.5Fe0.5O3) to elongated he- xagonal(SmCr0.5Mn0.5O3), and finally to well-edged rectangular(SmCr0.17Mn0.5Fe0.33O3) plates. Fe and Mn doped SmCrO3 crystals are indexed into Pbnm space group. The cell parameters of SmCr0.5Fe0.5O3 are slightly smaller than that of pristine SmCrO3. Binding energy analysis of Cr, Mn and Fe in SmCr0.17Mn0.5Fe0.33O3 sample indicates that they all possess +3 oxidation states. Temperature dependent magnetization of the as-prepared samples presents obviously stronger ferromagnetic interactions than the undoped counterparts. This work represents a remarkable development for hydrothermal synthesis into fabricating perovskite oxide crystals with uniform distribution of doping ions.

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WANG Jingyang, ZHANG Meng, XU Xiaodong, FENG Jing, WANG Yanli, ZHANG Milin, HAN Wei, CHEN Yitung, TIAN Guoxin
Synthesis and Characterization of [Cu(N-MeIm)4(BF4)2] in Ionic Liquid
2018 Vol. 34 (1): 8-12 [Abstract] ( 1 ) [HTML 1KB] [PDF 0KB] ( 4 )   
doi: 10.1007/s40242-018-7259-2

A new transition metal complex, [Cu(N-MeIm)4(BF4)2](N-MeIm=N-methylated imidazoles, BF4= tetrafluoroborate), was synthesized via the solvothermal method in ionic liquid. The ionic liquid acts as thermal decomposition reaction medium, soft temple agent and ligand compound. The central Cu(II) ion is coordinated by four N atoms from four N-methylated imidazole ligands, and the four N-methylated imidazole rings are perpendicular to each other. The crystal structure of [Cu(N-MeIm)4(BF4)2] was determined by single crystal X-ray diffraction. The results of thermogravimetry(TG) and Fourier transform infrared spectrometry(FTIR) analyses were in accordance with that of crystal structure. The complex showed strong ligand-based absorbance with maximum wavelength at 208 and 231 nm, which are attributed to π-π* transition of the N-methylated imidazole ligands.

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WANG Qi, YANG Xiaohui, JIANG Yanqiu, HUO Hang, LI Defeng, LIN Kaifeng, XU Xianzhu
Easily Separated and Recyclable Amino-functionalized PorousSiO2 Beads with 3D Continuous Meso/Macropore Channels
2018 Vol. 34 (1): 13-18 [Abstract] ( 1 ) [HTML 1KB] [PDF 0KB] ( 4 )   
doi: 10.1007/s40242-018-7208-0

Amino-functionalized porous SiO2 beads with a diameter of 200—800 μm(PSB-NH2) have been successfully synthesized by grafting 3-aminopropyl-triethoxysilane onto meso/macroporous silica beads(PSB), in which the PSB was prepared by hydrothermal synthetic method with a porous hard template anion-exchange resin. The as-prepared materials were characterized by means of nitrogen sorption and transmission electron micrographs(TEM), showing the presence of 3D interconnected and continuous large mesopores and macropores inside. The beads were used to catalyze Knoevenagel condensation and proved to be highly active and selective due to the high accessibility of the reactants to the amino groups via the continuous 3D meso/macopores. Notably, such material in bead format facilitates the extremely straightforward separation from reaction solution without any centrifugation or filtration. Moreover, PSB-NH2 proved to be a stable catalyst via leaching experiment test, and can be easily recovered and reused without significant loss of activity in successive catalytic cycles.

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LUO Yansheng, ZENG Xuehua, WANG Wanman, CHEN Jinglin, HE Lihua, ZHANG Mengli, LIU Suijun, WEN Herui
Emissive Mononuclear Cu(I) Triphenylphosphine Complexes with Functionalized 6-tert-Butoxycarbonyl-2,2'-bipyridine
2018 Vol. 34 (1): 19-23 [Abstract] ( 1 ) [HTML 1KB] [PDF 0KB] ( 3 )   
doi: 10.1007/s40242-018-7201-7

Two new emissive mononuclear copper(I) triphenylphosphine complexes with functionalized 6-tert- butoxycarbonyl-2,2'-bipyridine chelating ligands were prepared and characterized. Each Cu(I) cation has a markedly distorted P2N2 tetrahedral array with two different Cu—N bond distances, due to the addition of the bulky tert-butoxycarbonyl group at the 6-position of the 2,2'-bipyridyl ring. A weak low-energy broad absorption band appears at 330—500 nm in their CH2Cl2 solutions, which is influenced by the methylation of the 2,2'-bipyridyl ring. At room temperature, the photoluminescence can be clearly observed both in degassed CH2Cl2 solution and in the solid state, because of the introduction of the bulky tert-butoxycarbonyl substituent, and the emission properties are remarkably affected by both the methylation and the alkoxycarbonyl variation of the 2,2'-bipyridyl ring. It is shown that the introduction of the bulky tert-butoxycarbonyl group is favorable for improving the emission properties of the 6-alkoxycarbonyl-2,2'-bipyridine-based cuprous complexes.

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TAN Wenjia, SUN Zhixia, XUAN Lili, LI Junling, XIE Wenbing, HE Chengyan, PAN Lihua
Development of BCPDA-Eu3+-BAS Labeled Hepatitis B Surface Antibodies
2018 Vol. 34 (1): 24-27 [Abstract] ( 1 ) [HTML 1KB] [PDF 0KB] ( 4 )   
doi: 10.1007/s40242-018-7295-y

The effect of the chelating agent 4,7-bis(chlorosulfophenyl)-1,10-phenanthroline-2,9-dicarboxylic acid (BCPDA) labeled hepatitis B surface antibodies(HBsAb) on time-resolved fluoroimmunoassays(TRFIA) was investigated. The labeling detection method was established. The biotin-streptavidin(BAS) system was introduced, and the multi-stage amplification effect of the BAS system was analyzed. It is found that the BCPDA-Eu3+-HBsAb-BAS fluorescent marker can emit strong fluorescence. Compared to BCPDA-Eu3+-HBsAb, BCPDA-Eu3+-HBsAb-BAS demonstrates an enhanced fluorescence intensity by over 10 times. This study provides a guidance for the next gene- ration non-radio immunoassays in clinical diagnosis.

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ZHANG Hong, ZOU Li, LI Ruimin, ZHAO Mingqin, LING Liansheng
Hairpin Probe for Sequence-specific Recognition of Double-stranded DNA on Simian Virus 40
2018 Vol. 34 (1): 28-32 [Abstract] ( 1 ) [HTML 1KB] [PDF 0KB] ( 3 )   
doi: 10.1007/s40242-017-7152-4

Simian virus 40(SV40) is a polyomavirus and can induce a series of different tumors. The recognition of SV40 genome is crucial to tumor diagnosis and gene therapy. Herein, a sensitive and selective colorimetric method for sequence-specific recognition of homopyrimidine·homopurine duplex DNA(dsDNA) of SV40(4424—4440, gp6) was established with a hairpin probe based upon the formation of triplex DNA. Hairpin probe 5'-CCC TAC CCA TTT TTT CTT CTC TTT CCT GGG TAG GGC GGG TTG GG-3'(HP) containing G-rich sequence and 17-bp triplex-forming sequence was used as the signal probe, which was stem-loop structure alone and exhibited low catalytic activity. Upon its binding to the target duplex of SV40, hairpin probe transferred from stem-loop structure to parallel triplex DNA, accompanied by the recovery of catalytic activity of DNAzyme and a sharp increase of absorbance. Under optimum conditions, the absorbance was increased proportionally to the concentration of dsDNA over the range from 500 pmol/L to 40.0 nmol/L with a detection limit of 433 pmol/L. Moreover, satisfied results were obtained when the assay was used to recognize the mismatched sequences.

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ZHAO Ying, FU Zhijing, CHEN Xiaofei, ZHANG Guoyan
Bioremediation Process and Bioremoval Mechanism of Heavy Metal Ions inAcidic Mine Drainage
2018 Vol. 34 (1): 33-38 [Abstract] ( 1 ) [HTML 1KB] [PDF 0KB] ( 4 )   
doi: 10.1007/s40242-018-7255-6

Acidic mine drainage(AMD) containing acidity and a broad range of heavy metal ions is classified as hazardous, and must be properly treated. The removal mechanism of heavy metal ions in acidic mine drainage contai- ning Cu2+, Fe2+, and Zn2+ with biological method was studied here. Using 20 mmol/L ethanol as carbon source, Desulfovibrio marrakechensis,one of sulfate reducing bacteria(SRB) species, grew best at 35 ℃ and pH=6.72 with concentrations of 10, 55 and 32 mg/L for Cu2+, Fe2+ and Zn2+, respectively. The removal efficiency for each ion mentioned above was 99.99%, 87.64% and 99.88%, respectively. The mineralogy and surface chemistry of precipitates were studied by means of energy dispersive spectrometer(EDS), X-ray photoelectron spectroscopy(XPS), X-ray diffraction(XRD) combined with control tests. The experimental results demonstrate that the removal mechanism of heavy metal ions by Desulfovibrio marrakechensis is comprehensive function of chemical precipitation, adsorption and bioprecipitation. The biogenic iron sulfide solid was characterized as greigite(Fe3S4), while the zinc sulfide solid was characterized as sphalerite(ZnS).

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SHI Chenfei, LI Yumeng, FENG Haiyao, JIA Shumin, XUE Ruijie, LI Gang, WANG Guoxiang
Removal of p-Nitrophenol Using Persulfate Activated by Biochars Prepared from Different Biomass Materials
2018 Vol. 34 (1): 39-43 [Abstract] ( 1 ) [HTML 1KB] [PDF 0KB] ( 4 )   
doi: 10.1007/s40242-017-7245-0

Three biochars from wheat straw(WSC), chicken manure(CMC) and rice husk(RHC) were prepared as persulfate(PS) activators for p-nitropheol(PNP) removal. RHC exhibitted the best adsorption performance, followed by WSC and CMC, which was consistant with the surface area value. PS addition further promoted the PNP removal, indicating that a synergistic effect existed in the biochar/PS combined system. The composition and textual properties of biochar had a significant effect on the reactivity of activator and the function groups containing oxgygen or nitrogen might play important roles in the reaction. WSC could perform efficiently over a pH range from 4.4 to 10.4. The decrease in activation performance in cycle experiments was possiblely related to the loss of oxgygen-containing groups.

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CHEN Like, LIU Miao, LENG Su, LI Zhuan
A Comparative Toxicity Study of TiO2 Nanoparticles in Suspension and Adherent Culture Under the Dark Condition
2018 Vol. 34 (1): 44-50 [Abstract] ( 1 ) [HTML 1KB] [PDF 0KB] ( 4 )   
doi: 10.1007/s40242-018-7193-3

The present study focused on the different acute toxicity of TiO2 nanoparticles(TiO2 NPs) towards the bacteria in suspension culture and adherent culture under the dark conditions. The study investigated the bacteria toxicity with TiO2 NPs at different concentrations(1—2000 mg/L), sizes(10 nm, 35 nm) and specific surface areas in unit volume solution(0—224 m2/L) characterized by the cell viability, extracellular polymeric substances(EPS) release and biofilm formation. The bacteria in adherent culture was found to be more resistant against the toxicity of TiO2 NPs compared to that in suspension culture. An NP dose and surface area dependent(rather than the size) bacterial viability was observed in suspension culture, specifically the surface area positively correlated with the toxicity of TiO2 NPs. The size of TiO2 NPs, however, played a more critical role in toxicity of TiO2 NPs in adherent culture. Therefore, the surface area dependent toxicity of TiO2 NPs is a comprehensive parameter describing the dose and size dependent toxicity of TiO2 NPs. The electron microscopic(SEM, TEM, EDX) observations suggested the EPS release and biofilm formation, during aggregation of TiO2 NPs on the bacteria after 12 h cultivation in adherent culture under the dark condition. A possible toxic mechanism could be that “effective surface areas” that directly contact with the bacterial membrane greatly contributed to the toxicity of TiO2 NPs in both suspension culture and adherent culture. Therefore, as for the possible resistance mechanism, EPS secretion and subsequent biofilm formation may protect the bacteria against the toxicity of TiO2 NPs.

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XU Boxuan, DING Xiudong, WU Yachuang, CUI Lei, QIAN Ping, WANG Di, ZHAO Yanfang
Synthesis and Antibacterial Activity of Oxazolidinone Derivatives Containing Nitro Heteroaromatic Moiety
2018 Vol. 34 (1): 51-56 [Abstract] ( 1 ) [HTML 1KB] [PDF 0KB] ( 3 )   
doi: 10.1007/s40242-018-7302-3

A series of novel oxazolidinone derivatives containing nitro heteroaromatic moiety was synthesized and characterized by means of 1H NMR and MS spectra. All target compounds were evaluated for their in vitro antibacterial activities against S.au 29213, methicillin-resistant Staphylococcus aureus(MRSA) and vancomycin-resistant Enterococcus(VRE) by minimum inhibitory concentration(MIC) assay. Most of them exhibited antibacterial activity against S. au 29213, MRSA and VRE. Among them, compounds 10e and 10f displayed better activity than the control.

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ZHENG Renhua, HUANG Qing, GUOHaichang, HUANGYidie, JIANG Huajiang
Gold-catalyzed Intermolecular Oxidation of Phenylacetylene and Allylic Sulfides: an Efficient and Practical Synthesis of α-Phenylthio Ketone
2018 Vol. 34 (1): 57-60 [Abstract] ( 1 ) [HTML 1KB] [PDF 0KB] ( 5 )   
doi: 10.1007/s40242-018-7238-7

An efficient and practical synthesis of α-phenylthio ketone through gold-catalyzed intermolecular oxidation of phenylacetylene and substituted aryl(benzyl) allylic sulfides was developed. The reaction scope is fairly good with substituted aryl(benzyl) allylic sulfides, tolerating various functional groups, and the reaction affords the yields of 63%—85%.

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YAO Hua, WANG Tong, WU Qian, LIU Ying, LI Peng, LI Xuwen, JIN Yongri
Studies on New Steroidal Saponins from Allii macrostemonis Bulbus and Their Antitumor Activities
2018 Vol. 34 (1): 61-66 [Abstract] ( 1 ) [HTML 1KB] [PDF 0KB] ( 4 )   
doi: 10.1007/s40242-018-7213-3

Two new steroidal saponins(2, 3) and two known compounds(1, 4) were isolated from 75% ethanol extract of Allii macrostemonis bulbus by various spectral methods. The two new steroidal saponins were respectively elucidated as (25S)-26-O-β-D-glucopyranosyl-5α-furostanol-2α,3β,22,26-tetrol-3-O-β-D-glucopyranosyl(1→2)-[β-D- glucopyranosyl(1→3)]-β-D-glucopyranosyl(1→4)-β-D-galactopyranoside(2) and 26-O-β-D-glucopyranosyl-5α- furostanol-25(27)-ene-3β,22,26-tetrol-3-O-β-D-glucopyranosyl(1→2)-[β-D-glucopyranosyl(1→3)]-β-D-glucopyranosyl- (1→4)-β-D-galactopyranoside(3). Compound 4 was obtained from this medical plant for the first time. The activity experiments of proliferation inhibition on tumor cells were performed by cell counting kit-8(CCK-8) method for compound 2(25S-configuration) and its isomer(compound 1, 25R-configuration). The results show that compounds 1 and 2 have weak inhibition on lung cancer A549 cells, melanoma A375 cells and breast cancer MCF-7 cells as well as certain inhibitory effect on liver cancer HepG2 cells, and the inhibitory effect of compound 1 is stronger than that of compound 2.

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WANG Shihui, SONG Yuming, WANG Yue, GAO Yang, YU Shanshan, ZHAO Qianqian, JIN Xiangqun, LU Haibin
Studies on New Steroidal Saponins from Allii macrostemonis Bulbus and Their Antitumor Activities Design and Synthesis of Novel Bispecific Molecules for InducingBRD4 Protein Degradation
2018 Vol. 34 (1): 67-74 [Abstract] ( 1 ) [HTML 1KB] [PDF 0KB] ( 3 )   
doi: 10.1007/s40242-018-7272-5

Proteolysis targeting chimeras(PROTACs) are bispecific molecules containing a target protein binder and a ubiquitin ligase binder connected by a linker. Recently, some heterobifunctional small molecule bromodomain-containing protein 4(BRD4) degraders based on the concept of PROTACs were designed to induce the degradation of BRD4 protein. Herein, we synthesized a new class of PROTAC BRD4 degraders. One of the most promising compound 22f exhibited robust potency of BRD4 inhibition with IC50 value of (9.4±0.6) nmol/L. Furthermore, compound 22f potently inhibited cell proliferation in BRD4-sensitive cell lines RS4;11 with IC50 value of (27.6±1.6) nmol/L and capable of inducing degradation of BRD4 protein at 0.5―1.0 μmol/L in the RS4;11 cells. These data establish that compound 22f is a potent and efficacious BRD4 degrader.

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XU Qihao, YU Shujia, CAI Yijun, YANG Jinyu, ZHAO Linxiang, LIU Dan
Design, Synthesis and Biological Evaluation of Novel Selective Thiol-based Histone Deacetylase(HDAC) VI InhibitorsBearing Indeno[1,2-c]pyrazole or Benzoindazole Scaffold
2018 Vol. 34 (1): 75-83 [Abstract] ( 1 ) [HTML 1KB] [PDF 0KB] ( 5 )   
doi: 10.1007/s40242-018-7239-6

A series of thiol-based indeno[1,2-c]pyrazoles and benzoindazole compounds was designed and synthesized according to the structural specificity of histone deacetylase VI(HDAC6) and the structural characteristics of HDAC inhibitors. The inhibitory activities of the target compounds against HDAC6 and HDAC1 were screened by fluorescence analysis. Most of the target compounds showed moderate inhibitory activity against HDAC6(IC50=44—598 nmol/L). Among them, compound A-4 displayed the highest selectivity against HDAC6 and similar inhibitory activity(IC50=44 nmol/L) to that of the positive drug SAHA(IC50=41 nmol/L) against HDAC6.

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SU Yuhan, QI Xuefei, TIAN Jun, LIN Chenhui, CHEN Ligong, LI Yang, JIN Yuehua, YAN Xilong, WANG Bowei
Wang Resin-supported Enantioselective Catalysts for the Asymmetric Michael Additions ofAcetone to β-Nitroolefins
2018 Vol. 34 (1): 84-89 [Abstract] ( 1 ) [HTML 1KB] [PDF 0KB] ( 4 )   
doi: 10.1007/s40242-018-7189-z

Two Wang resin-supported (1R,2R)-(+)-1,2-DPEN(DPEN=diphenylethylenediamine) catalysts were synthesized from cyanuric chloride and trimesoyl chloride, respectively. These two catalysts were characterized by FTIR, TGA and elemental analysis. The results demonstrated that (1R,2R)-(+)-1,2-DPEN was successfully bonded to the surface of Wang resin through the amido linkage. Subsequently, the asymmetric Michael addition of acetone to β-nitrostyrene was employed to evaluate their catalytic performance. It was found that the catalyst generated from trimesoyl chloride exhibited much better catalytic behavior than our previously reported catalyst, likely attributed to the multiple hydrogen-bond interaction between β-nitrostyrene and amide group, which made the catalytic transition intermediates more stable. Under the optimal conditions, 76.1% β-nitrostyrene conversion and 93.8% enantioselectivity were obtained. Finally, the generality of this catalyst was examined with Michael additions of acetone to β-nitroolefins and excellent enantioselectivities(91.9% to 99.9%) were achieved.

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HE Wei, ZHAO Anran, ZOU Jiajia, LUO Xuan, LIN Xiao, WANG Lisheng, LIN Cuiwu
Synthesis, In vitro Coagulation Activities and Molecular Docking Studies on Three L-Histidine Amide Derivatives
2018 Vol. 34 (1): 90-94 [Abstract] ( 1 ) [HTML 1KB] [PDF 0KB] ( 5 )   
doi: 10.1007/s40242-018-7184-4

Three novel L-histidine amide derivatives were synthesized and the corresponding chemical structures were characterized by means of melting point analysis, IR, MS, 1H NMR as well as 13C NMR. The coagulation acti- vities of the compounds were evaluated by an MOE(molecular operating environment) docking technique and coagulation test. The results obtained from molecular docking show that the interactions between the compounds and thrombin exhibit procoagulant activity in combination with an improved combinatory effect. Moreover, the results of in vitro coagulation tests show that the L-histidine amide derivatives feature coagulant activities in common coagulation pathways. Compared with the blank control group, the optimal shortening rates of compounds 13 were 39.08%(0.5 mmol/L), 22.94%(1.0 mmol/L) and 15.38%(0.0625 mmol/L), respectively.

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FU Xianwei, LIU Yang, LIU Zhi, DONG Ning, ZHAO Tianyu, ZHAO Dan, LIAN Gang, WANG Qilong, CUI Deliang
Pressure-sensitive Transistor Fabricated from an OrganicSemiconductor 1,1'-Dibutyl-4,4'-bipyridinium Diiodide
2018 Vol. 34 (1): 95-100 [Abstract] ( 1 ) [HTML 1KB] [PDF 0KB] ( 5 )   
doi: 10.1007/s40242-018-7297-9

Although organic semiconductors have attracted extensive interest and been utilized to fabricate a variety of optoelectronic devices, their electrical transportation characteristics under high pressure have rarely been investigated. However, the weak intermolecular interaction of organic semiconductors endows them with a pre- ssure-sensitive crystal structure and electrical transportation performance, especially the latter. Herein, a new pre- ssure-sensitive transistor was fabricated from an organic semiconductor 1,1'-dibutyl-4,4'-bipyridinium diiodide. It was found that this transistor exhibited increasing resistance as the pressure gradually increased and that it eventually shut off under a pressure of 288 MPa. Such a characteristic makes this organic semiconductor a potential candidate for the use in the fabrication of pressure-sensitive switches and regulators. In addition, these results shed light on the electrical performance of flexible organic optoelectronic devices working under high pressure levels resulted from the bending force.

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LU Wenjie, XU Rongjin, ZHANG Xinai, SHEN Jianzhong, LI Changfeng
Electrochemical Immunoassay of E. coli in Urban Sludge Using Electron Mediator-mediated Enzymatic Catalysis and Gold Nanoparticles for Signal Amplification
2018 Vol. 34 (1): 101-106 [Abstract] ( 1 ) [HTML 1KB] [PDF 0KB] ( 5 )   
doi: 10.1007/s40242-017-7254-z

An electrochemical immunosensor was developed for sensitive assay of E. coli in urban sludge, in which electron mediator-mediated enzymatic catalysis and gold nanoparticles(AuNPs) were utilized for signal amplification. The immnuosensing platform chitosan-thionine(chit-thio)/poly(amidoamine) dendrimer-encapsulated AuNPs [PAMAM(Au)] composites were first prepared from chit-thio and PAMAM(Au) using the layer-by-layer method to provide a matrix for high-stability and high-bioactivity bindings of the capture antibody(cAb). Moreover, the {dAb-AuNPs-HRP} nanoprobes were designed to exploit the amplification effect of the carrier AuNPs due to the loading amounts of horseradish peroxidase(HRP) and the detection antibody(dAb). The sandwich-type immunoassay was then successfully used to assay E. coli based on the oxidation of thionine as a result of H2O2-induced enzymatic catalytic reaction by HRP. This study presents a powerful tool in electrochemical immunoassay for E. coli detection with rapid response, high-sensitivity and high-specificity, providing a potential new tool for feasibility assessment of sludge recycle.

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WANG Shanshan, HAN Wei, ZHANG Milin, LI Mei, YANG Xiaoguang, SUN Yang
Electrochemical Behaviour of Magnesium(II) on Ni Electrode inLiCl-KCl Eutectic
2018 Vol. 34 (1): 107-112 [Abstract] ( 1 ) [HTML 1KB] [PDF 0KB] ( 4 )   
doi: 10.1007/s40242-018-7227-x

The electrochemical behaviour of magnesium(II) and the formation mechanism of Mg-Ni alloys on Ni electrode were studied in LiCl-KCl eutectic using various electrochemical techniques. Cyclic voltammogram and square-wave voltammogram revealed that under-potential deposition of magnesium occurred on Ni electrode because Mg-Ni alloy compounds were formed. The thermodynamic properties of the Mg-Ni intermetallics, Mg2Ni and MgNi2, were determined using open circuit chronopotentiometry in the temperature range of 818―893 K. Moreover, the Mg-Ni alloys were produced by potentiostatic and galvanostatic electrolysis under different conditions and characterized by means of scanning electron microscopy(SEM) equipped with energy dispersive spectrometry(EDS) and X-ray diffraction(XRD). The experimental results indicate that Mg-Ni intermetallic compounds can be selectively produced by potentiostatic electrolysis.

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Ana Maria POPESCU, Kazimir YANUSHKEVICH, Vasile SOARE, Cristina DONATH, Elena Ionela NEACSU, Virgil CONSTANTIN
Recovery of Metals from Anodic Dissolution Slime of Waste from Electric and Electronic Equipment(WEEE) by Extraction in Ionic Liquids
2018 Vol. 34 (1): 113-118 [Abstract] ( 2 ) [HTML 1KB] [PDF 0KB] ( 4 )   
doi: 10.1007/s40242-017-7225-4

The recovery of metals from a multi-component alloy obtained by crushing, melting and anodic dissolution of waste from electric and electronic equipment(WEEE) was investigated. The anodic dissolution of the alloy was carried out in an electrolysis cell with one copper cathode and a central cast anode, immersed in the electrolyte formed by choline chloride-ethylene glycol-iodine. The temperature of the electrolyte during the process was 343 K. Depending on the electrolysis parameters(current density and cell voltage), cathodic deposits of Sn, Pb and Zn of >99% purity were obtained. Cyclic voltammetry was used in order to determine the deposition potentials of the studied metals. The obtained metallic deposits were subject of determination of XRD, SEM/EDX and AFM in order to evidence the deposits structure and morphology. The experiments performed demonstrated the possibility of separating/selective recovery of metals from the multi-component alloy resulted from the waste from electrical and electronic equipment by anodic dissolution in ionic liquids.

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YU Ke, DIAO Tingting, ZHU Junjiang, ZHAO Zhen
Perovskite Oxides La0.8Sr0.2Co1-xFexO3 for CO Oxidation and CO+NO Reduction: Effect of Redox Property and Surface Morphology
2018 Vol. 34 (1): 119-126 [Abstract] ( 2 ) [HTML 1KB] [PDF 0KB] ( 4 )   
doi: 10.1007/s40242-018-7156-8

This work aims to study the effect of redox property and surface morphology of perovskite oxides on the catalytic activity of CO oxidation and CO+NO reduction, with the redox property being tuned by doping Fe at the Co site of La0.8Sr0.2Co1-xFexO3 and the surface morphology being modified by supporting La0.8Sr0.2CoO3 on various mesoporous silicas(i.e., SBA-16, SBA-15, MCF). Characteristic results show that the Fe doping improves the match of redox potentials, and SBA-16 is the best support of La0.8Sr0.2CoO3 when referring to the oxidation ability(e.g., the Co3+/Co2+ molar ratio). A mechanism for oxygen desorption from perovskite oxides is proposed based on O2-TPD experiments, showing the evolution process of oxygen released from oxygen vacancy and lattice framework. Catalytic tests indicate that La0.8Sr0.2CoO3 is the best for CO oxidation, and La0.8Sr0.2FeO3 is the best for CO+NO reduction. The mechanism of CO+NO reduction changes as the reaction temperature increases, with XNO/XCO value decreases from 2.4 at 250 ℃ to 1.0 at 400 ℃. As for the surface morphology, La0.8Sr0.2CoO3 supported on SBA-16 possesses the highest surface Co3+/Co2+ molar ratio as compared to the other two, and shows the best activity for CO oxidation.

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LI Shuang, LI Shuni, ZHAI Quanguo, JIANG Yucheng, HU Mancheng
Phase Behavior of Ionic Liquids-Cesium Carbonate-Water Aqueous Two-phase Systems and Their Extraction of L-Tryptophan
2018 Vol. 34 (1): 127-131 [Abstract] ( 1 ) [HTML 1KB] [PDF 0KB] ( 5 )   
doi: 10.1007/s40242-018-7148-8

Phase behavior and extraction ability of aqueous two-phase systems(ATPs) consisting of ionic liquids(ILs), Cs2CO3 and water were investigated in this paper. Four kinds of ionic liquids, namely, 1-amyl-3-methylimidazolium bromide([C5mim]Br), 1-hexyl-3-methylimidazolium bromide([C6mim]Br), 1-heptyl-3-methylimidazolium bromide ([C7mim]Br) and 1-octyl-3-methylimidazolium bromide([C8mim]Br), were examined to discuss the influence of alkyl groups. Binodal curves and tie-lines at 288.15, 298.15 and 308.15 K were obtained. The partitioning behavior for L-tryptophan in such ATPs was further investigated. The effect of temperature, pH, Cs2CO3 concentration and the structure of ionic liquids on the partitioning were discussed in detail.

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SUN Rui, WANG Ying, GOU Pengfei, ZUO Min, LI Xiaodong, ZHU Weipu, SHEN Zhiquan
Amphiphilic Seven-arm Star Triblock Copolymers with Diverse Morphologies in Aqueous Solution Induced by Crystallization and pH
2018 Vol. 34 (1): 132-137 [Abstract] ( 1 ) [HTML 1KB] [PDF 0KB] ( 4 )   
doi: 10.1007/s40242-017-7218-3

Well-defined amphiphilic seven-arm star triblock copolymers containing hydrophobic crystalline poly(ε-caprolactone)(PCL) blocks, hydrophobic non-crystalline poly(tert-butyl acrylate)(PtBA) blocks and hydrophilic poly(ethylene glycol)(PEG) blocks were precisely synthesized by a combination of ring-opening polymerization(ROP), atom transfer radical polymerization(ATRP) and “click” reaction. Such star copolymers could self-assemble into “core-shell-corona” micelles and “multi-layer” vesicles depending on the fraction of each block. Meanwhile, the selective hydrolysis of middle PtBA blocks into the poly(acrylic acid)(PAA) blocks allowed the star block copolymers to further change their morphologies of aqueous aggregates in response to pH values.

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DONG Lei, LIU Huan, LI Yanjuan, ZHANG Hongtao, YU Liangmin, JIA Lanni
Template Effect of Hydrophobically Associating Polymers on theConstruction of Cuprous Oxide Micro Structure
2018 Vol. 34 (1): 138-144 [Abstract] ( 1 ) [HTML 1KB] [PDF 0KB] ( 3 )   
doi: 10.1007/s40242-018-7173-7

To determine the template effect of hydrophobically associating copolymers(HACPs) on the morphology of nano/micro structures, six HACPs were synthesized and used as templates to biomimetically synthesize cuprous oxide(Cu2O), an important semiconductor. This experiment showed a clear relationship between the associating state of the HACP molecules and the morphology of the Cu2O particles. Cu2O hollow spheres were preferentially prepared when the HACP molecules were in an intramolecular associating state. Furthermore, a Cu2O hexapod was easily obtained when the HACP molecules were in an intermolecular associating state. The morphologies of the Cu2O crystals prepared in the presence of the HACPs also confirmed this result.

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ZHANG Chunyu, DONG Bo, ZHANG Hexin, HU Yanming, ZHANG Xuequan
Morphology and Properties of PP In-reactor Alloys Prepared with a MgCl2/TiCl4/Diisobutyl Phthalate/Phosphate Tris-methylphenyl Ester Catalyst System
2018 Vol. 34 (1): 145-150 [Abstract] ( 1 ) [HTML 1KB] [PDF 0KB] ( 4 )   
doi: 10.1007/s40242-017-7140-8

A series of polypropylene(PP)/poly(ethylene-co-propylene) in-reactor alloys with different ethylene contents was prepared through a two-stage polymerization process using a MgCl2/TiCl4/diisobutyl phthalate/phosphate tris-methylphenyl ester catalyst system. The ethylene content, particle shape, fractured surface, and glass-transition temperature(Tg) of the obtained PP in-reactor alloys were characterized by means of nuclear magnetic resonance, scanning electron microscopy(SEM), and dynamic mechanical analysis(DMA). The ethylene content of the PP alloys increased from 2.34% to 26.69% when the propylene/ethylene feed ratio was increased from 66/34 to 54/46(molar ratio). Morevoer, the increment in ethylene content increased the notched Izod impact strength of the resulting PP alloys. The impact strength of the PP alloy with an ethylene content of 26.69% was 55.8 kJ/m2, which is 12.7 times that of isotactic polypropylene. The results of DMA and SEM analysis reveal that ethylene-propylene random copolymer(EPR) in the PP alloy has a low Tg of ca. -50 ℃ and a high interface compatibility with the PP matrix. The excellent impact performance of the PP alloy can be attributed to the uniform dispersal of EPR in the alloy particles and PP matrix.

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ZHU Xiaofei, ZHANG Xiaodong, HUANG Lizhen, WANG Zi, CHI Lifeng
Improving the Performance of TIPS-pentacene Thin FilmTransistors via Interface Modification
2018 Vol. 34 (1): 151-154 [Abstract] ( 2 ) [HTML 1KB] [PDF 0KB] ( 4 )   
doi: 10.1007/s40242-017-7122-x

Understanding the structure-performance relationship is crucial for optimizing the performance of organic thin film transistors. Here, two interface modification methods were applied to modulate the thin film morphology of the organic semiconductor, 6,13-bis(triisopropylsilylethynyl)pentacene(TIPS-pentacene). The resulting different film morphologies and packing structures led to distinct charge transport abilities. A substantial 40-fold increase in charge carrier mobility was observed on the octadecyltrichlorosilane(OTS)-modified sample compared to that of the transistor on the bare substrate. A better charge mobility greater than 1 cm2·V-1·s-1 is realized on the p-sexiphenyl(p-6P)- modified transistors due to the large grain size, good continuity and, importantly, the intimate π-π packing in each domain.

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