Table of Content

10 March 2015, Volume 36 Issue 3

Previous Issue    Next Issue

Content

Cover and Content of Chemical Journal of Chinese Universities Vol.36 No.3(2015)

2015, 36(3):  0-0. 

Asbtract ( )   PDF (16082KB) ( )  

Related Articles | Metrics

Review

Research Progress of Intelligent CO₂-Responsive Materials^†

TIAN Tong, LI Jinghui, WANG Yao

2015, 36(3):  399-410.  doi:10.7503/cjcu20141024

Asbtract ( )   HTML ( )   PDF (6676KB) ( )  

Figures and Tables | References | Related Articles | Metrics

Intelligent CO₂-responsive materials were kinds of new materials of which the physical structures or chemical properties will reversibly change when they were triggered by CO₂.These novel CO₂-responsive materials attracted wide attentions of scientists due to their characteristic CO₂-responsive mechanism and highly efficient transitional properties. In this review, the preparation methods and their application of the recent CO₂-responsive materials based on amino groups and amidine groups were reviewed, respectively. Meanwhile, the development prospect of the novel CO₂-responsive materials was also discussed.



Articles: Inorganic Chemistry

Synthesis, Characterization and Blue-emission of Cd(Ⅱ)Coordination Polymers with μ-Chlorine-Bridging One-dimensional Chain Structures^†

HUANG Jian, LIU Zhigang, FAN Ruiqing, DONG Yuwei, ZHANG Huijie, WANG Yulei, YANG Yulin

2015, 36(3):  411-419.  doi:10.7503/cjcu20140986

Asbtract ( )   HTML ( )   PDF (4717KB) ( )  

Figures and Tables | References | Related Articles | Metrics

Two coordination polymers, {[Cd(mpep)]Cl₂}_n(1, mpep=2-{1-[(2-methylphenyl)imino]-ethyl}pyridine) and {[Cd(acpy)]Cl₂}_n(2, acpy=2-acetylpyridine), were synthesized under solvothermal condition. The structures of complexes 1 and 2 were characterized by single crystal X-ray diffraction analysis, ¹H nuclear magnetic resonance(¹H NMR) spectrometry, elemental analysis and infrared(IR) spectrometry. The results show that both complexes 1 and 2 have 1D chain structure. The central cadmium(Ⅱ) atom in complex 1 is coordinated by four chloride ions and two nitrogen atoms from mpep, forming a distorted cis-octahedron coordination geometry, and the Cd(mpep)]Cl₂ unit builds up a polymeric chain by μ₂-chlorine-bridging. The central cadmium(Ⅱ) atom in complex 2 is coordinated by a nitrogen atom and an oxygen atom from acpy and four chloride ions, forming a distorted cis-octahedron coordination geometry, the Cd(acpy)]Cl₂ unit builds up a polymeric chain by μ₂-chlorine-bridging. Additionally, the fluorescent properties of the two complexes were characterized in both solid state and in different polar solvents. The results show that com-plexes 1 and 2 exhibit blue fluorescence emission(ca.390—433 nm) in CH₃OH, CH₃CN and CH₂Cl₂, indicating that the coordination polymers have weak solvent effect. The emission spectra of complexes 1 and 2 at 298 K are centered at 440 and 473 nm respectively in solid state. Comparing to the emission spectra in solutions, the emission spectra in solid-state undergo obvious red-shift. The lifetime of complexes 1 and 2 are relatively long(ca.19.08—60.20 μs) at room temperature.



Influences of Metal Oxide Encapsulation by Atomic Layer Deposition on the Sensitivities of Octogen^†

QIN Lijun, GONG Ting, HAO Haixia, WANG Keyong, FENG Hao

2015, 36(3):  420-427.  doi:10.7503/cjcu20141009

Asbtract ( )   HTML ( )   PDF (2596KB) ( )  

Figures and Tables | References | Related Articles | Metrics

Micron-scale Octogen(HMX) particles were coated by alumina and zinc oxide thin films via atomic layer deposition(ALD). The surface chemical compositions and morphologies of ALD metal oxides coated HMX particles were characterized by X-ray photoelectron spectroscopy(XPS) and scanning electron microscopy(SEM). The thermal decomposition behaviors of the fabricated HMX particles were analyzed by differential scanning calorimetry(DSC) and thermogravimetry(TG) techniques. The mechanical sensitivity and electrostatic spark sensitivity of the metal oxides coated HMX were tested. The influences of film composition and thickness on the sensitivities of HMX were analyzed. The results indicate that the HMX particles are completely and uniformly encapsulated by ALD alumina or zinc oxide thin films. The thickness of the encapsulation layer can be precisely controlled in nanometer-scale. The thin films of metal oxides have little influence on the thermal decomposition properties of HMX. Due to the hardness of the metal oxides, ALD encapsulation layers do not decrease the mechanical sensitivity of HMX. However, the inorganic ALD coatings increase the surface electrical conductivity of HMX particles and therefore reduce the electrostatic spark sensitivity.



Influence of F^- on the Structure-directing Effect of Organic Amines in the Synthesis of Open-framework Aluminophosphates^†

TIAN Ye, WANG Shurong, YAN Wenfu, XU Ruren, WANG Yongrui, MU Xuhong

2015, 36(3):  428-435.  doi:10.7503/cjcu20140894

Asbtract ( )   HTML ( )   PDF (1735KB) ( )  

Figures and Tables | References | Related Articles | Metrics

The significant influence of F^- on the structure-directing effect of ethylenediamine(en) and diethylenetriamine(deta) in the synthesis of open-framework aluminophosphates was investigated. For the system with ethylenediamine, in the absence of F^-, layered aluminophosphate Al₂P₂O₉·NH₃(CH₂)₂NH₃(UiO-13) was obtained from the initial mixture with n(Al₂O₃):n(P₂O₅):n(en):n(H₂O)=1.0:1.5:18.0:147 under hydrothermal condition, while layered aluminophosphate AlF(HPO₄)·NH₂(CH₂)₂NH₂(1) was obtained from the initial mixture with n(Al₂O₃):n(P₂O₅):n(en):n(HF):n(H₂O)=1.0:1.5:18.0:3.0:147. The results suggested that the F^- significantly affected the structure-directing effect of ethylenediamine. For the system with diethylenetriamine, a three-dimensional(3D) open-framework aluminophosphate Al₄P₅O₂₀(H₂O)₂·C₄N₃H₁₆(AlPO-CJ31) was synthesized from the initial mixture with n(Al₂O₃):n(P₂O₅):n(deta):n(H₂O)=1.0:4.0:3.0:153 under hydrothermal condition, while a one-dimensional(1D) aluminophosphate Al₂P₄O₁₀(OH)₃F·C₄N₃H₁₅(2) was crystallized from the similar initial mixture in the presence of F^-[n(Al₂O₃):n(P₂O₅):n(deta):n(HF):n(H₂O)=1.0:4.0:3.0:3.0:153]. The results indicated that the structure-directing effect of diethylenetriamine was significantly altered by F^-. The structural properties of open-framework aluminophosphates UiO-13, 1, AlPO-CJ31 and 2 were analyzed in detail and the influence of F^- on the structure-directing effect of ethylenediamine and diethylenetriamine was discussed.



Preparation of β-MnO₂ and α-Mn₂O₃ Nanorods via a Self-sacrificing Template Route and Their Characterization and Application^†

ZHAO Hongyuan, LIU Xingquan, ZHANG Zheng, WU Yue, YANG Guang, CHEN Bing, XIONG Weiqiang

2015, 36(3):  436-441.  doi:10.7503/cjcu20140670

Asbtract ( )   HTML ( )   PDF (2133KB) ( )  

Figures and Tables | References | Related Articles | Metrics

Pure-phased γ-MnOOH nanorods were synthesized at 150 ℃ for 20 h through a hydrothermal reaction process, during which KMnO₄ was reduced by CH₃CH₂OH under autogeneror pressure. With γ-MnOOH nanorods as self-sacrificing template, β-MnO₂ and α-Mn₂O₃ nanorods were prepared by calcining at 350 and 600 ℃ for 90 min, respectively. The materials were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM) and thermal-gravimetric analysis(TGA). The results showed that γ-MnOOH nanorods had good crystallographic quality and the diameters were about 100—300 nm, the length could be as long as several micrometers. The morphology and microstructure were well reserved in β-MnO₂ and α-Mn₂O₃ products and no other morphology of impurities was observed. With β-MnO₂ and α-Mn₂O₃ nanorods as manganese sources, spinel LiMn₂O₄ samples were prepared by solid state method. At the charge/discharge rate of 0.5 C, the LiMn₂O₄ samples could deliver the initial discharge capacities of 120.4 and 123.9 mA·h/g, respectively, and present good cycling stability and rate performance.



Analytical Chemistry

Effect of Schisandra Fruit on Neurochemicals in Hippocampus of Diabetic Encephalopathy Rat Using Online MD-HPLC-MS/MS^†

PI Zifeng, WANG Qianqian, ZHANG Jing, Song Fengrui, LIU Zhiqiang

2015, 36(3):  442-448.  doi:10.7503/cjcu20140813

Asbtract ( )   HTML ( )   PDF (1087KB) ( )  

Figures and Tables | References | Related Articles | Metrics

The results of morris water maze test showed that the extract of schisandra fruit could significantly shorten the escape latency time(ELT) and increase the time of crossing target zone and central zone(%) of diabetic encephalopathy rats. In order to investigate the mechanism of schisandra fruit on the improving ability of learning and memory, online MD-HPLC-MS/MS method was applied to explore the effect of schisandra fruit on eight neurochemicals changes in hippocampus of diabetic encephalopathy rats. The results showed that the contents of Glu, Ser, DA and 5-HT decreased significantly(P<0.05), while the contents of Tau and Ach increased significantly(P<0.01) after treated by schisandra fruit. The contents of Asp and GABA tended to decrease but the difference was not significant(P>0.05). The levels of eight neurochemicals regulated to normal level. The results indicated that schisandra may play a protective function of the central nervous system by adjusting the contents of neurochemicals in diabetic rats, which can improve the memory and learn ability of diabetic encephalopathy rat.



Preparation and Application of Magnetic Bisphenol A Imprinted Polymers with Binary Functional Monomers^†

RAO Wei, YIN Yuli, LONG Fang, ZHANG Zhaohui

2015, 36(3):  449-455.  doi:10.7503/cjcu20140764

Asbtract ( )   HTML ( )   PDF (2171KB) ( )  

Figures and Tables | References | Related Articles | Metrics

A kind of magnetic molecularly imprinted polymers(mag-MIPs) was synthesized by heated polymerization technique using bisphenol A(BPA) as template, β-cyclodextrin(β-CD) and 4-vinylpyridine(4-VP) as the binary functional monomers. The mag-MIPs were characterized by means of transmission electron microscopy(TEM), Fourier transform infrared spectroscopy(FTIR) and vibrating sample magnetometer(VSM). Adsorption experiments indicated that the mag-MIPs prepared with β-CD and 4-VP exhibited high selectivity toward BPA. The performance of the mag-MIPs used as magnetic solid-phase extraction(M-SPE) sorbent was evaluated, and the results showed that it could selectively extract BPA from water samples. The imprinted magnetic solid-phase extraction method has been applied for preconcentration and purification of BPA from water samples with the recoveries range of 90.51%—98.21%.



Interaction of GABA Receptor in the Fish Brain with Ro7-1986/1 and Fipronil by Fluorescent-labeled Ligand^†

YANG Shan, ZHANG Bo, ZHANG Yuan, REN Tianrui

2015, 36(3):  456-463.  doi:10.7503/cjcu20140942

Asbtract ( )   HTML ( )   PDF (1994KB) ( )  

Figures and Tables | References | Related Articles | Metrics

Two kinds of γ-aminobutyric acid(GABA) receptor ligands, Ro7-1986/1 and Fipronil, were explored for preparing fluorescein conjugates including FITC-Ro7-1986/1 and FITC-Fipronil. Fourier transform infrared spectroscopy(FTIR) and ¹H NMR were used to characterize the structures of the synthesized products. The interactions between GABA receptor in hypophthalmichthys nobilis brain and both ligands were studied by fluorescence-labeling method. In addition, the effects of GABA on the binding of Ro7-1986/1 and GABA receptors were also investigated. The results showed that the equilibrium dissociation constants(K_d) and the maximum number of binding sites [RT] between Ro7-1986/1 and receptor were (67±5) nmol/L and (13.8±1.8) pmol/mg protein, respectively. The values of K_d and [RT] between Fipronil and receptor were (346±6) nmol/L and (40.6±3.5) pmol/mg protein, respectively. Meanwhile, GABA was able to significantly elevate the binding of between ligand and receptor, which indicated the pharmacological properties of GABA receptor in fish brain are remarkably similar to those in mammalian brain. Moreover, Fipronil exhibited more excellent affinities to fish by comparison to mammals.



Organic Chemistry

Syntheses and Biological Activities of V-Shaped Symmetrical Triazolothiazine Oxadiazole Derivatives^†

ZHANG Chenglu, WANG Xue, HU Xue, SUN Lijie, QU Ruifeng, GUO Yang, CHAI Jinhua, ZHU Chang’an

2015, 36(3):  463-468.  doi:10.7503/cjcu20140918

Asbtract ( )   HTML ( )   PDF (2867KB) ( )  

Figures and Tables | References | Related Articles | Metrics

To build V-shaped symmetrical structure thiadiazole derivatives, isophthalic acid and 5-aminoisophthalic acid condensed with 3-aliphatic-1,2,4-triazole(1) respectively. In POCl₃ presence, fourteen symmetrical V-shaped triazolo-thiadiazole derivatives(2a—2g and 3a—3g) were synthesized, wherein thirteen of them were first synthesized, and the structures of compounds 2 and 3 were characterized by infrared(IR), nuclear magnetic resonance(NMR) and high resolution mass spectrometer(HRMS). The inhibitory activities of the target compounds were screened for Cdc25B and PTP1B. The results showed that some compouds exhibited inhibitory activities against Cdc25B, compounds 3b and 3f may be used as potential Cdc25B inhibitors in the treatment of cancer. Compouds 3b—3g exhibited inhibitory activities against PTP1B. Compounds 3b and 3e may be used as potential PTP1B inhibitors in the treatment of diabetes.



Synthesis, Antibacterial Activity and Molecular Simulation with FabⅠ of a Series of Novel 1,2,4-Triazolo[3,4-b]-1,3,4-thiadiazoles^†

WANG Meijun, LU Junrui, XIN Chunwei, LIU Jinbiao, MU Jiangbei, ZHANG He, ZHANG Ruibo, YANG Xuyun, WANG Hongyun

2015, 36(3):  469-476.  doi:10.7503/cjcu20140907

Asbtract ( )   HTML ( )   PDF (1832KB) ( )  

Figures and Tables | References | Related Articles | Metrics

Ten novel compounds of 3-alkyl/aryl-6-S-(2',3',4',6'-tetra-O-acetyl-β-D-glcopyranosyl)-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazoles were designed and synthesized from 3-alkyl/aryl-4-amino-5-mercapto-1,2,4-triazoles. The structures of all the compounds were confirmed by means of ¹H NMR, ¹³C NMR, HRMS and IR. The preliminary bioassay showed that all target compounds possessed efficient antibacterial activities on Escherichia coli, Staphylococcus aureus, Bacillus subtilis and Monilia albican. Especially, the compound 3c had strong antibacterial by the lowest minimal inhibitory concentration(MIC) values on the four tested strains which were close to those of the controlled drug fluconazole. The interaction and binding free energy of the target compounds(3a—3j) with FabⅠ were studied by AutoDock 4.0.



Synthesis and Anion Recognition of Trinuclear Ferrocene-based Imidazole Receptors^†

ZHUO Jibin, WAN Qian, YAN Xiquan, XIE Lili, YUAN Yaofeng

2015, 36(3):  477-483.  doi:10.7503/cjcu20140819

Asbtract ( )   HTML ( )   PDF (1527KB) ( )  

Figures and Tables | References | Related Articles | Metrics

Anions are ubiquitous in the world and play important roles in modern chemistry and life process, numerous efforts have been devoted to the design of acyclic receptors capable of selectively binding and sensing anions. Herein, several novel trinuclear ferrocene-based imidazole receptors 2a—2c were synthesized from the reactions of 1-(ferrocenylmethylene)imidazole with corresponding bromides 1a—1c. All of these receptors were characterized by ¹H NMR, ¹³C NMR, MS, IR and elemental analysis. The anion binding studies were carried out by various techniques such as electrochemistry(CV and DPV) and ¹H NMR spectroscopy. Electrochemical behavior indicated that all the receptors displayed unique electrochemical sensing property for F^- with a remarkable phenomenon: the previous peak of the free receptor gradually diminished, a new wave at more negative potential(ΔE_p>-150 mV) appeared due to the hydrogenation reaction. ¹H NMR titrations demonstrated that all the receptors could bind anions through(C—H)⁺…anion hydrogen bonds forming 1:1 stoichiometric complexes and had good fluoride binding ability in DMSO-d₆. Addition of F^- caused deprotonation effect on the receptors, indicating the receptors showed better affinity for F^-. Particularly, receptor 2b turned out to be a very good anion receptor with remarkably high preference in binding with F^-.



Synthesis, Characterizations and Electroluminescent Properties of Luminescent Diphenylamino Substituted Acridine Derivatives^†

CHEN Dong, ZHANG Xueqiang, ZHANG Jingying, WANG Yue

2015, 36(3):  484-488.  doi:10.7503/cjcu20140797

Asbtract ( )   HTML ( )   PDF (1522KB) ( )  

Figures and Tables | References | Related Articles | Metrics

Two fluorescent acridine derivatives were designed and synthesized for the fabrication of organic light-emitting diodes(OLEDs). By attaching diphenylamino substituent groups to the acridine core, the energy levels and molecular packing structures of them were regulated and controlled. Moreover, OLEDs using these compounds as emitters were fabricated, they all exhibited green emission and low turn-on voltages of 2.4 V were realized. They achieved the highest power efficienciey(PE) as high as 4.9 and 8.2 lm/W together with the peak current efficiency(CE) values of 5.3 and 7.4 cd/A, respectively. These results represent very high EL performance based on the simple HTL-EML-ETL architecture from fluorescent organic emitters. The photophysical, electrochemical and thermal properties of the two compounds were also studied, the results proved that acridine derivatives possess promising potential for the application of high-performance fluorescent OLEDs.



Reduction Selectivity of 2-Substituted Cyclododecanone and Conformation Analysis of trans-1,2-Disubstituted Cyclododecanes^†

YANG Mingyan, ZHANG Li, WANG Daoquan, WANG Ming'an

2015, 36(3):  489-498.  doi:10.7503/cjcu20140798

Asbtract ( )   HTML ( )   PDF (2331KB) ( )  

Figures and Tables | References | Related Articles | Metrics

To confirm the cis-selectivity on the reduction of 2-substituted cyclododecanone and analyze the preferred conformation of trans-1,2-disubstituted cyclododecanes, the reduction of 2-phenyl/cyclohexylcyclododecanones were carried out at the different reductive reagents and temperatures. Based on these results, a series of trans-1,2-disub- stituted cyclododecanes was prepared via NaBH₄ reduction of 2-substituted cyclodode- canones, ring-opening of cyclododecene oxide, Mitsunobu reaction of cis-2-phenyl cyclododecanol and hydrolysis, their preferred conformation were analyzed on the basis of ¹H NMR, ¹³C NMR, X-ray diffraction and quantum chemistry calculation. The results showed that the preferred conformations of trans-1,2-disubstituted cyclododecanes were [3333] square conformation, in which the one group presents at the side-exo position and the other one at the corner-anti. The X-ray diffraction structures of the reductive products of cis-2,12-disubstituted cyclododecanones showed that 1,2,3-trisubstituted cyclodode- canes still take [3333] square conformation, in which the two groups present at the side-exo positions and the hydroxy at the corner-syn, three groups are cis-cis relationships.



Effect of Organic Acid Treatment on Microalgae Lipid Extraction^†

WANG Songmei, KUAN Dingyaw, DU Wei, ZHAO Xuebing, LIU Dehua

2015, 36(3):  499-504.  doi:10.7503/cjcu20140707

Asbtract ( )   HTML ( )   PDF (1029KB) ( )  

Figures and Tables | References | Related Articles | Metrics

Developing an advanced cell treatment technology is very important for promoting microbial oils as the feedstock for biodiesel production. The traditional inorganic acid-heat treatment process has some problems such as difficulty in recycling inorganic acid, serious environmental pollution and so on. This paper explores using organic acid which is easy to recycle, to treat cells for lipid extraction from microalgae. Effect of formic acid treatment on lipid extraction from Chlorella protothecoides was investigated systematically. The results showed that formic acid was very effective in treating microalgae cells and the total lipid yield and fatty acid methyl esters(FAME) yield were comparable with those obtained from inorganic acid-heat treatment process. It was found that formic acid concentration, temperature, treatment time and liquid/solid ratio(l/s) had a significant influence on micro-algae lipid extraction. Under the optimum condition of formic acid concentration 88%, temperature 100 ℃, treatment time 30 min and ratio of liquid to solid 6:1, the total lipid yield and FAME yield reached 49.2% and 92.1%, respectively. There was no obvious difference in fatty acid composition in the microbial oils obtained from organic acid treatment and inorganic acid-heat treatment process. There were 5 kinds of fatty acid in the microbial oil from Chlorella protothecoides, among which the content of C18:1 was the highest. Then, the adaptation of formic acid treatment to different microalgae material was investigated. The results showed that the total lipid yield and FAME yield of Nannochlorum sp and Nannochloropsis Oceanic were comparable with those obtained from inorganic acid-heat treatment process.



Syntheses and Antimicrobial Activities of 4-Substituted Phenyl 1,5-Benzothiazepines-2-carboxylic Acids

WANG Jiao, TIAN Keqing, XUE Ziqiao, WU Yunyun, YANG Tian, ZHAO Huimin, ZHANG Ping

2015, 36(3):  505-510.  doi:10.7503/cjcu20140588

Asbtract ( )   HTML ( )   PDF (534KB) ( )  

Figures and Tables | References | Related Articles | Metrics

It was reported the products of α,β-unsaturated carboxylic acid and o-aminothiophenol with acid catalyst were seven-membered ring benzothiazepins containing a carboxyl group. Subsequent literature suggested that the structure of the reaction product was a six-membered ring lactam structure. According to the reported method we carried out the reaction and the products obtained were not the reported seven-membered ring benzothiazepin structure, but the six-membered ring lactam structures 3a—3k, which structures were confirmed by mapping and crystal structure analysis. Under the different experimental conditions, we obtained seven-membered ring benzothiazepins 2a—2k, and found that compounds 2a—2k could converted to its isomers six-membered ring lactam 3a—3k. The structures of compounds 2a—2k were confirmed by IR, ¹H NMR, ¹³C NMR, MS and elemental analysis. Antibacterial activity tests showed that compounds 2a—2k had good antibacterial activity against Candida albicans, Cryptococcus neoformans(standard and clinical), E. coli and B. subtilis. While compounds 3a—3k had no activities of the measured strains. It was noteworthy that the mixtures of compounds 2a—2e and 3a—3e had better antifungal effects than those of compounds 2a—2e single, the presence of compound 3a—3e enhanced the antibacterial activities of compounds 2a—2e.



Labeling and Purification of Alcalase and Fluorescent Nanocrystals Synthesized in Water Phase^†

ZHU Jinming, SUN Zhuo, FU Yao, GUO Yi, XU Li

2015, 36(3):  511-515.  doi:10.7503/cjcu20140803

Asbtract ( )   HTML ( )   PDF (1748KB) ( )  

Figures and Tables | References | Related Articles | Metrics

CdTe nanocrystals were synthesized in aqueous solution and capped with amercaptopropionic acid, which were used as a kind of fluorescent probe to label Alcalase. The fluorescence spectra showed that CdTe nanocrystals were accompanied by a narrow size distribution and high stability. The fluorescence intensity decreased 8.36% after 30 d at room temperature. Transmission electron microscopy(TEM) imaging revealed that CdTe nanocrystal’s diameter was about 3 nm, and X-ray diffraction(XRD) pattern showed it with zinc blende structure. After being conjugated with Alcalase using 1-ethyl-3-(3-dimethyl aminopropye) carbodii-mide hydroclloride(EDC) and N-hydroxysulfosucinimide sodium salt(NHSS) methods, the CdTe-Alcalase conjugates were separated and purified by ultra-filter-centrifugation, a Sephadex G-100 column and sodium dedecye sulfate(SDS)-polyacrylamide gel electrophoresis. Fluorescent spectral analysis showed that CdTe-Alcalase conjugates also presented good optical stability compared with CdTe nanocrystals. The enzyme activity was also relatively high at 61.06 U/μg. The fluorescent emission of the CdTe-Alcalase conjugates was visualized with a fluorescence microscope, which would be suitable for tracing the enzyme reaction in the future.



Physical Chemistry

Mechanism Study on the Interaction Between 2'-Hydroxy-2,4-dibromo Diphenyl Ethers and Human Serum Albumin Based on Spectroscopic Methods and Computional Simulations^†

DONG Lu, YI Zhongsheng, WU Zhiwei, WANG Haiyang, ZHANG Aiqian

2015, 36(3):  516-522.  doi:10.7503/cjcu20141007

Asbtract ( )   HTML ( )   PDF (2780KB) ( )  

Figures and Tables | References | Related Articles | Metrics

The interaction between 2'-hydroxy-2,4-dibromo diphenyl ethers(2'-OH-BDE-7) and human serum albumin(HSA) was investigated with molecular docking, molecular dynamics simulation and spectroscopy techniques. The results of synchronous fluorescence spectroscopy indicated that the conformation of HSA was changed when 2'-OH-BDE-7 binding to HSA, which consistent with the results of molecular dynamics simulations. In addition, the results of fluorescence spectroscopy experiment showed that the intrinsic fluorescence quenching of HSA was reduced by 2'-OH-BDE-7. Static quenching and non-radiation energy transfer are the two main reasons leading to the fluorescence quenching of HSA by 2'-OH-BDE-7. In the process of binding, the entropy, the enthalpy and the Gibbs free energy were negative, which suggested that the interaction between 2'-OH-BDE-7 and HSA was driven mainly by hydrophobic forces and van de Waals forces. Finally, a similar conclusion was obtained from the competitive experiment and molecular docking, which shown 2'-OH-BDE-7 binded human serum albumin at site Ⅰ. Excellent agreement was founded between computer simulations results and spectral experiments to provide more information for the mechanism study on the interaction between 2'-OH-BDE-7 and HSA.



Promotional Effect of Pr-Doping on the NH₃-SCR Activity over the V₂O₅-MoO₃/TiO₂ Catalyst^†

CHAO Jingdi, HE Hong, SONG Liyun, FANG Yujiao, LIANG Quanming, ZHANG Guizhen, QIU Wenge, ZHANG Ran

2015, 36(3):  523-530.  doi:10.7503/cjcu20140895

Asbtract ( )   HTML ( )   PDF (2890KB) ( )  

Figures and Tables | References | Related Articles | Metrics

V₂O₅-MoO₃/Pr₆O₁₁-TiO₂ catalysts were prepared by means of an impregnation method and TiO₂ supports doped with different amounts of Pr were synthesized via a sol-gel method. The evaluation of selective catalytic reduction(SCR) activity indicated the catalysts with high activity and N₂ selectivity in a temperature range of 220—400 ℃. And the Pr-doped catalyst also exhibited good resistance to SO₂ and H₂O. The catalysts were characterized by means of X-ray diffraction(XRD), N₂ adsorption-desorption(BET), X-ray photo-electron spectrometer(XPS) and in situ diffuse reflectance infrared Fourier transform spectroscopy(in situ DRIFTS). The results showed that the specific surface areas of Pr-doped V₂O₅-MoO₃/TiO₂ catalysts were larger than that of the V₂O₅-MoO₃/TiO₂ catalyst. Furthermore, the addition of Pr on V₂O₅-MoO₃/TiO₂ catalyst could give more NH₃ adsorption species, chemisorbed oxygen species, bridged nitrate species and the numbers of Brönsted acid sites, resulting in an enhance in the catalytic activity for NH₃-SCR of NO_x.



Mechanisms and Kinetics of the Synthesis of FOX-12^†

WANG Kuan, CHEN Jiangang, WANG Bozhou, LU Jian, WANG Wenliang, LIU Fengyi, ZHOU Cheng, LIAN Peng, LIU Zhongwen, LIU Zhaotie

2015, 36(3):  531-538.  doi:10.7503/cjcu20140873

Asbtract ( )   HTML ( )   PDF (2723KB) ( )  

Figures and Tables | References | Related Articles | Metrics

The mechanisms of the synthesis of N-guanylurea-dinitramide(FOX-12) were investigated at B3LYP/6-311G(d,p) level. The geometries of the reactants, intermediates, transition states, and products were optimized, respectively. The relevance between every transition state and the corresponding reactant/product was confirmed via the intrinsic reaction coordinates(IRC). The single-point energies of the species at the optimized geometries were corrected at the MP2/6-311++G(3df,3pd) level. It was shown that the binitro-amide acid(HDN) could be obtained by both channel A1, in which —SO₃ was preferentially replaced by nitronium(N\begin{array}{c}{O}_2^{+}\end{array}), and channel B, in which —H was preferentially replaced by N\begin{array}{c}{O}_2^{+}\end{array}, while the channel A1 was found to be the dominant channel. Then the intermediate product of HDN could be converted to the targeted product of FOX-12 via the channel of either HDN→FOX-12 or HDN→amonium dinitramide(ADN)→FOX-12, while the latter was tend to be considered as the better approach. The rate constants were calculated at temperature ranges of 200—400 K by means of the classical transition state theory(TST) and the canonical vibration transition state theory(CVT) corrected by the small-curvature tunneling(SCT). And the three-parameter Arrhenius expressions of rate constants were also provided. It was expected that the present study may provide a theoretical basis to the research and engineering amplification of FOX-12 as well as other energetic materials.



Thermodynamic Functions of Nano Zinc Oxide Acquired by Microcalorimetry and Electrochemical Methods^†

LIU Xiaolin, WANG Lude, HUANG Zaiyin, LIU Zuojiao, LI Xingxing

2015, 36(3):  539-543.  doi:10.7503/cjcu20140814

Asbtract ( )   HTML ( )   PDF (1587KB) ( )  

Figures and Tables | References | Related Articles | Metrics

Nano zinc oxide(ZnO) hierarchical structures with uniform size and morphology were prepared by microemulsion-mediated hydrothermal route. The thermodynamic functions at 298.15 K, such as standard molar enthalpy, standard molar Gibbs free energy, and standard molar entropy of the synthesized nano ZnO were obtained by employing microcalorimetry and electrochemical method, individually. Microcalorimety for acquiring thermodynamic functions of nanomaterial was mainly based on that nano reaction system and its corresponding bulk reaction system possess the same transition state, whereas electrochemical method for acquiring thermodynamic functions of nanomaterial was mainly based on the difference of electrode potential between nanomaterial and its corresponding bulk material. The results reveal that the thermodynamic functions obtained by microcalorimetry and electrochemical method are approximately equal in the range of allowable error. The results also proved that both of the two developed methods to obtain thermodynamic functions of nanomaterials are effective and scientific. Moreover, it further support that the nano ZnO reaction system and its correspon-ding bulk ZnO reaction system experience the same transition state.



Supercritical Fluid Extraction of Direct Coal Liquefaction Residue Basing on Hansen Solubility Parameters^†

JIANG Guangce, LIN Xiongchao, ZHANG Shengjuan, WANG Zhongqi, WANG Yonggang, CHEN Qiang, ZHU Yufei

2015, 36(3):  544-550.  doi:10.7503/cjcu20140705

Asbtract ( )   HTML ( )   PDF (1711KB) ( )  

Figures and Tables | References | Related Articles | Metrics

The supercritical fluid extraction(SFE) of direct coal liquefaction residue using acetone, isopropanol and benzene as solvents was investigated. The Hansen solubility parameters were used to clarify the variations of both solvent and the solute in SFE process. An empirical equation in terms of the extended Hansen approach was proposed to correlate the extraction capacity with the Hansen solubility parameters of solvents. The results show that the extraction yield using supercritical benzene, of which the dispersive component is the major in total solubility parameters, obtained the highest extraction yield. The ideal solubility on organic components in direct coal liquefaction residue improved with the extraction temperature increasing. The empirical equation shows high consistency with experimental results. As a consequence, the theory of Hansen solubility parameter and extended Hansen approach are applicable to the study on supercritical fluid extraction of direct coal liquefaction residue.



In-situ Synthesis of BiOCl/NaBiO₃ Composites and Their Photocatalytic Activities^†

JI Lei, YU Ruimin, WANG Haoren, CHEN Liduo, WANG Huaiyuan

2015, 36(3):  551-558.  doi:10.7503/cjcu20140694

Asbtract ( )   HTML ( )   PDF (3972KB) ( )  

Figures and Tables | References | Related Articles | Metrics

BiOCl/NaBiO₃ composite photocatalytic materials were in-situ synthesized through the reaction of NaBiO₃ and HCl. The phase structures, surface morphologies and optical properties of the samples were studied by X-ray powder diffraction(XRD), scanning electron microscope(SEM) and UV-Vis diffuse reflectance spectra(UV-Vis DRS), respectively. The photocatalytic activities of the samples were evaluated by degradation of rhodamine B(RhB) under visible and ultraviolet light, respectively. Under visible light the 27.4%(molar fraction) BiOCl/NaBiO₃ shows higher photocatalytic activity than the pure BiOCl and NaBiO₃; under ultraviolet light all the BiOCl/NaBiO₃ composites show higher photocatalytic activities than pure BiOCl and NaBiO₃. The results indicate that the composition of BiOCl and NaBiO₃ can form heterojunction region, and then influence the transfer behavior of photogenerated carriers. The photocatalysis experiments with different trapping agents and terephthalic acid photoluminescence(TA-PL) suggest that ·OH played major role for RhB degradation. A possible mechanism involving charge separation process between BiOCl and NaBiO₃ was proposed. The n-p type heterojunction at the interface between p-BiOCl and n-NaBiO₃ can efficiently reduce the recombination of photogenerated electron-hole pairs, which accounts for the enhancement of photocatalytic activity. From the analysis of potential, it is theoretically deduced that the photocatalytic degradation of RhB could be attributed to the ·OH and hole rather than ·\begin{array}{c}{O}_2^{-}\end{array} radicals.



Polymer Chemistry

In-situ Intercalative Polymerization of Poly(lactic acid)/HTCC-saponite Nanocomposites and Their Properties Characterization^†

XI Xi, ZHEN Weijun, BIAN Shenzhen

2015, 36(3):  559-567.  doi:10.7503/cjcu20141059

Asbtract ( )   HTML ( )   PDF (5887KB) ( )  

Figures and Tables | References | Related Articles | Metrics

Water-soluble N-(2-hydroxyl)propyl-3-trimethyl ammonium chitosan chloride(HTCC) was synthesized with 2,3-epoxypropyl trimethyl ammonium chloride(GTA) grafting to the amino groups of chitosan by two-step method. Then, chitosan quaternary ammonium intercalated saponite(HTCC-saponite) was synthesized with HTCC and saponite under ultrasonication. Moreover, poly(lactic acid)(PLA)/HTCC-saponite nanocomposites were prepared by means of in-situ intercalative polymerization with HTCC-saponite and lactide. Orthogonal experiment showed the optimization polymerization parameters of PLA/HTCC-saponite were as follows: the polymerization temperature was 150 ℃, the amount of stannous caprylate was 2%(mass fraction), the amount of HTCC saponite was 1%(mass fraction) and the polymerization time was 16 h. The morphology analysis showed that the HTCC-saponite appeared with intercalative or partially exfoliated structure. The microstructure, morphology and thermal properties of PLA/HTCC-saponite nanocomposites were characterized by XRD, TEM, TG-DTG and DSC, respectively. The results showed that HTCC-saponite obviously promoted the crystallinity and thermal stability of PLA. The antibacterial results showed that HTCC-saponite had good antimicrobial properties, which was endowed in PLA/HTCC-saponite nanocomposites.



N435 Enzymatic Degradation Difference and Molecular Modeling of Hydrophilic Modified PBS-based Copolymer^†

ZHANG Min, ZHANG Yi, LI Chengtao, QIN Jiaxiang, Gao Rang, MA Xiaoning, QIU Jianhui

2015, 36(3):  568-574.  doi:10.7503/cjcu20140966

Asbtract ( )   HTML ( )   PDF (2756KB) ( )  

Figures and Tables | References | Related Articles | Metrics

By lipase Novozym435, enzymatic degradation of copolymers poly(butylene succinate-diglycolic butanediol)ester[P(BS-co-BDGA)] and poly(butylene succinate-diethylene glycol succinate)ester[P(BS-co-DEGS)] which contain ether oxygen bond at different positions of alcohol binding segment and acid binding segment in the main chain of PBS, was performed in the aqueous system. And molecular docking simulations explore the recognition of enzyme on hydrophilic substrate and the interaction mechanisms. In order to study the degradation law of PBS modified copolymers, the mass loss rate, hydrophilicity and thermal properties of the copolymer films and the degradation products were investigated. The results show that: with the passage of time, mass loss rate of the copolymer films is increased, increasing the hydrophilicity and the thermal decomposition temperature; after degradation for 5 d, oligomeric species of P(BS-co-BDGA) are more than P(BS-co-DEGS). Combined with the results of molecular docking, P(BS-co-BDGA) ester bond of ether bond in an acid binding segment docking with the Novozym435 enzyme active sites is more stable than P(BS-co-DEGS) ester bond of ether bond in an alcohol binding segment, so under the action of the enzyme. The degradation effect of P(BS-co-BDGA) is better than P(BS-co-DEGS); and in the synthesized composition range, when the addition amount of DGA is 20%(molar fraction), degradation effect is best.



Copolymerization of Norbornene and n-Butyl Methacrylate Catalyzed by Novel Ni(Ⅱ)(benzocyclohexan-ketoarylimino) ₂ ^†

HE Xiaohui, LIU Jingyin, CHEN Lu, ZHU Hongyu, WANG Juan

2015, 36(3):  575-580.  doi:10.7503/cjcu20140932

Asbtract ( )   HTML ( )   PDF (1748KB) ( )  

Figures and Tables | References | Related Articles | Metrics

Vinyl-addition copolymerization of norbornene(NB) and polar monomer n-butyl methacrylate(n-BMA) were carried out via two novel high activity catalysts, Ni(Ⅱ)(benzocyclohexan-ketoarylimino)₂ (Ni{C₁₀H₈(O)C[2,6-C₆H₃(CH₃)₂N]CH₃}₂, C1) and Ni{C₁₀H₈(O)C[2,6-C₆H₃Cl₂N]CH₃}₂, C2), in combination with tris(pentafluorophenyl)-borance[B(C₆F₅)₃]. A possible catalytic deactivation mechanism of polymerization was presented. Influence of monomer feed ratio on catalytic activity, conversion rate and properties of outcomes were investigated. Reactivity ratios of co-monomers were estimated by Kelen-Tüdõs method, they are r_n-BMA=0.02, r_NB=16.28, r_NB·r_n-BMA=0.32 for C1/B(C₆F₅)₃ catalytic system, and r_n-BMA=0.01, r_NB=64.83, r_NB·r_n-BMA=0.65 for C2/B(C₆F₅)₃ catalytic system. These indicate the random copolymerization of NB/n-BMA occurs with both C1/B(C₆F₅)₃ and C2/B(C₆F₅)₃.



Layer-by-layer Assembled Graphene/Polyaniline Nanocomposite Film and Applied in Electrochemical Sensing^†

SUN Jun, ZHU Zhengyi, LAI Jianping, LUO Jing, LIU Xiaoya

2015, 36(3):  581-588.  doi:10.7503/cjcu20140834

Asbtract ( )   HTML ( )   PDF (3871KB) ( )  

Figures and Tables | References | Related Articles | Metrics

A novel graphene-polyaniline nanocomposite thin film was prepared by means of electrostatic layer-by-layer(LBL) assembly of positive charged graphene sheets modified by poly(acrylic acid)(PAA-Gr) and negatively charged polyaniline(PANI). The use of PAA not only enhanced the dispersibility of the graphene sheets, but also provided a positive charge to the graphene thus facilitating the growth of multilayered films. Ultraviolet-visible spectrophotometry was used in the present work to monitor the LBL assembly process of {PAA-Gr/PANI}_n multilayered films. Fourier transform infrared spectroscopy, X-ray diffraction patterns, scanning electron microscopy and cyclic voltammetry results demonstrated the successful fabrication of {PAA-Gr/PANI}_n hybrid multilayered films. Application of the {PAA-Gr/PANI}_n hybrid film in electrochemical sensing was further demonstrated using H₂O₂ as a model analyte. The {PAA-Gr/PANI}_n hybrid film was shown to have excellent electrocatalytic activity towards H₂O₂. The proposed {PAA-Gr/PANI}_n film based sensor exhibited a wide linear detection range for H₂O₂ from 0.005 mmol/L to 0.3 mmol/L with a low detection limit of 1×10^-6 mol/L.



Preparation and Characterization of Chitosan Derivative Microspheres for Protein Delivery^†

LIU Yuanyuan, HUANG Yan, LU Zhengrong, BOAMAH Peter-Osei, ZHANG Qi, WU Jingbo, HUA Mingqing

2015, 36(3):  589-594.  doi:10.7503/cjcu20140665

Asbtract ( )   HTML ( )   PDF (3575KB) ( )  

Figures and Tables | References | Related Articles | Metrics

A novel amphiphilic narrow molecular weight distribution and low degree of polymerization lauryl-succinyl chitosan derivative(LSCOS) was synthesized in ionic liquid homogeneous system. The LSCOS microspheres were prepared according to water-in-oil emulsification cross-linking method with LSCOS as protein-loading material and bovine serum albumin(BSA) as a model protein and glutaraldehyde as the crosslinker. The effects of the BSA/LSCOS mass ratio and glutaraldehyde/LSCOS mass ratio on the morphology structure, loading capacity(LC), loading efficiency(LE) and in vitro BSA release characteristics were investigated by means of scanning electron microscopy(SEM), transmission electron microscopy(TEM) and UV-Vis spectroscopy. The results showed that LSCOS was successfully synthesized in ionic liquid and BSA-loaded LSCOS microspheres were spherical in shape with particle size approximately 1 μm. The microspheres had a smoother surface with the increasing ratio of BSA/LSCOS and a rougher surface with the increasing ratio of glutaraldehyde/LSCOS. Decrease and increase in the ratio of BSA/LSCOS and glutaraldehyde/LSCOS, respectively, resulted in the decrease of the cumulative release of BSA. The data indicated that protein release rate can be controlled by adjusting the protein ratio and the glutaraldehyde ratio. Therefore, the LSCOS synthesized in ionic liquid could be a promising material with slow-release function for protein delivery.