Table of Content

10 December 2011, Volume 32 Issue 12

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Contents

Cover and Content of Chemical Journal of Chinese Universities Vol.32 No.12(2011)

2011, 32(12):  0. 

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Volume Contents of Chemical Journal of Chinese Universities to Vol.32(2011)

2011, 32(12):  1. 

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Letters

Effect of Tension on the Microvoids Structure of Polyacylonitrile(PAN) Fibers During the Thermal Stabilization Stage

GAO Feng, ZHAO Jiang*

2011, 32(12):  2711-2713. 

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The effect of tension on the microvoids of polyacylonitrile(PAN)  thermal stabilized fibers was investigated by small angle X-ray scattering(SAXS) at Shanghai Synchrotron Radiation Facility(SSRF) at beamline BL16B. All SAXS patterns exhibit a very big anisotropy between the equator and meridian direction. The results indicate that the scattering bodies are elongated and oriented in direction of fiber axis. The quantitative parameters of orientation, length, diameter of the microvoids were obtained. The results show an obvious effect of tension to the microvoids' structure——a narrowing of the distribution of the microvoids misorientation and a more slender shape of microvoids, compared with the case without tension.



Synthesis of Soluble Polyazomethines Containing Triarylamine Units

ZHU Ming, LIU Xiao, LIU Bai-Jun*, JIANG Zhen-Hua

2011, 32(12):  2714-2716. 

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Based on a new diamine monmer, three polyazomethines containing triaylamine units were readily prepared through polycondensation reactions at room temperature. These polymers exhibit high Tg values(188—220 ℃), good thermal stability and improved solubility. The charge carrier mobility of the thiophene-containing polyazomethine could reach 1.94×10-4 cm2/(V?s).



Articles

MOCVD Preparation and Properties of ZnO and Ni\|doped ZnO Films

WANG Hui, WANG Jin, ZHAO Yang, ZHAO Long, ZHAO Wang, SHI Zhi-Feng, XIA Xiao-Chuan, MA Yan, DU Guo-Tong, DONG Xin*

2011, 32(12):  2717-2720. 

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ZnO and ZnO:Ni films were prepared by metal organic chemical vapor deposition method, and their structure and physical properties were studied. The surface morphologies and crystal structures of the films were analyzed by scanning electron microscope(SEM) and X-ray diffraction(XRD) technique. The results showed that doped Ni can affect the surface morphology and the crystal structure of the ZnO film greatly. The optical characteristic was performed by UV-Vis spectrophotometer. Average transmittance of the ZnO:Ni film was determined to be about 90% in the visible region, which is larger than that(85%)of the undoped ZnO film. The electrical characteristics were performed by Hall system. Resistivity of the ZnO:Ni film was larger than that of the undoped ZnO film. Carrier concentration of the ZnO:Ni film was much less than that of the undoped ZnO film.It was resulted from that Ni reduces the intrinsic donor defect concentration of ZnO film, and this avoids the strong self-compensate effect. Therefore, it is easier to acquire the p-type film by this way.



ZSM-5/SAPO-5 Composite Molecular Sieves Synthesized by Preloading Raw Material Method

ZHANG Qiang, LI Chun-Yi*, SHAN Hong-Hong, YANG Chao-He

2011, 32(12):  2721-2726. 

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ZSM-5(core)/SAPO-5(shell) binary structure composite molecular sieves were synthesized by preloading raw material method. The effect of loading conditions on the formation and character of core/shell structure zeolite was investigated. These synthesized samples were characterized by XRD, SEM, EDS and FTIR, respectively. The  results indicate that  the pretreated condition affects the combination of   phosphorus and ZSM-5,  the crystallinity and particle morphology of composite significantly.  Compared to hydrothermal synthesis method, this approach is helpful to forming smaller SAPO-5  particles and growing SAPO-5 on ZSM-5 surface under suitable pretreated condition.



Synthesis of Highly Emissive, Color\|tunable CdTe Quantum Dots in Aqueous Solution

WANG Yi-Lin*, HUANG Wu, WANG Rong-Fang, ZHOU Li-Ya

2011, 32(12):  2727-2732. 

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A novel technology was developed for the synthesis of mercaptosuccinic acid(MSA)-capped CdTe quantum dots(QDs) when sodium tellurite worked as a tellurium source and sodium borohydride acted as a reductant.  The influences of various experimental variables, including pH value, Cd/Te and Cd/MSA molar ratios, on the photoluminescence(PL) quantum yield(QY) of the prepared CdTe QDs were systematically investigated.  The obtained QDs were characterized by photoluminescence spectroscopy, X-ray powder diffraction(XRD) and transmission electron microscopy(TEM). The results show  that the CdTe QDs are of zinc-blended crystal structure in a sphere-like shape; various luminescent CdTe QDs with high emission efficiency(maximum quantum yield of 73.3%) can be prepared at pH=10.5 and n(Cd2+):n(Te2-):n(MSA)=1:0.05:1.4.



Synthesis and Characterization of a New Tailed Histidine-Linked Porphyrin

SHAN Ning, LIAN Wen-Hui, WANG Bin-Bin, SUN Yuan-Yuan, ZHENG Wen-Qi, YU Miao, SHI Tong-Shun*

2011, 32(12):  2733-2738. 

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A new histidine-linked porphyrin(1) and different transition metalloporphyrins[Zn(2), Co(3), Fe(4), Mn(5)] were prepared, purified and  characterized by means of elemental analysis, IR, UV-Vis and 1H NMR. The correlation between the structures of the complexes and their 1H NMR, IR, UV spectra was discussed and their specific spectra were explained. Their fluorescence characters were studied with the aid of fluorescence spectra and the lowest energy conformation  were chosen with 100 ps molecular dynamic simulation. The fluorescence intensity and the quantum yield of porphyrin 1 were low because of the electron\|withdrawing group on peripheral porphyrin ring. The fluorescence intensity and the quantum yield of   metalloporphyrin 2 were much weaker than those of the corresponding metal-free porphyrin 1 because zinc weakened the fluorescence radiation. Fluorescence signals had not been detected for metalloporphyrins 3—5 under the same experimental conditions  because of the fluorescence quenching. The mininal energy conformations and binding mode of four host-gust systems were obtained by molecular minimize and quantum chemistry. The four host-guest complexes were investigated to predicte the coordinate bond on four transition metal.



Preparation and Characterization of Wide-bandgap Cu(In, Al)Se2 Thin Films

HUANG Can-Ling, HU Bin-Bin, WANG Guang-Jun, LI Hong-Wei, GONG Shi-Jiang, DU Zu-Liang*

2011, 32(12):  2739-2742. 

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The precursor thin films of CuInSe2(CIS) were prepared using a special pulse electrodeposition method and Al was deposited on the CIS thin films through the vacuum evaporation method. The Cu(In, Al)Se2(CIAS) thin films were successfully fabricated by annealing the composite thin films of CIS and Al. The morphology, structure, composition and optical absorbance property of the CIAS thin films were characterized by  SEM, EDS, XRD, XPS and UV-Vis, respectively. The CIAS thin films composed of uniform particles present a chalcopyrite structure, and the surface is smooth and compact. The CIAS thin film has good absorption in the visible region, and the band gap is about 1.65 eV. 



Solvothermal Synthesis of Mesoporous TiO2 Spheres with Controllable Pore Size

HUANG Cai-Xia, GUO Ming-Yi, ZHANG Feng, SUN Fu-Xing, ZHU Guang-Shan*

2011, 32(12):  2743-2747. 

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We report a facile template-free method to fabricate monodisperse mesoporous TiO2 spheres using microporous titanium glycolates(TG) as precursor.  By solvothermal treatment, microporous TG can be directly converted into mesoporous TiO2 spheres via in-situ hydrolysis. The products  were characterized by XRD, SEM, TEM, FTIR and nitrogen absorption. The results show that the products exhibit high crystallinity, uniform morphology and tunable pore size. These integrated features would make the as-obtained mesoporous TiO2 materials have attractive applications in areas of environmental purification, energy conversion and storage.



Electrospray Ionization Mass Spectrometry Studies of Tetramolecular i-Motif Structures Formed by d(C4) Related Sequences

QIN Yu-Jiao, WEI Shi-Gang, WANG Xiao-Lu, YANG Fan, WANG Bing, GUO Xin-Hua*

2011, 32(12):  2748-2751. 

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A series of cytosine-rich DNA sequence d(C4) related DNA strands, including d(C4), d(TC4), d(AC4), d(T2C4), d(A2C4), d(C4T), d(C4A) and d(TC4T), was designed in this study, and the tetramolecular ions formed by the sequences were measured with electrospray ionization mass spectrometry. The goal is to obtain the information on the formation of the tetramolecular i-motif influenced by adenine(A) and thymine(T) that present at 5' and 3' ends of d(C4). The results showed that when A base or T base was added at 5' end of d(C4), it is easier for the sequence to form tetramolecular ion, especially for thymine, when adding two A or T bases to d(C4), the sequence generates higher abundant of the tetramolecualr ion.



Determination of four kinds of Monoester-diterpenoid aconines in SHEN-FU injection by homogeneous lonic liquid microextraction high-performance liquid chromatography

2011, 32(12):  2752-2756. 

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Abstract The determination of benzoylaconine(BA), benzoylmesaconine(BM), benzoylhypaconine(BH) and benzoyldeoxyaconine(BD) in SHEN-FU injection baced on homogeneous lonic liquid microextraction coupled with high-performance liquid chromatographic separation was described. The experimental parameters including volume of ionic liquid, pH, extraction time and salt concentration were optimizated, when 0.058g [C6Mim][ BF4] and 0.26g NH4PF6 were used as extraction solvent, the target compounds can be extracted from 5mL of injection, the extraction time is 1 min,neutral and the concentration of NaCl is 5%.The detection limits for BA,BM,BH and BD were 45.5,19.8,26.3 and 12.2,respectively. The recoveries of the analytes ranged from 93.74 to 107.91% and relative standard deviations were lower than 4.34%.



Articles

Preparation of New  Poly(α-D-galactopyranose) Chain-grafted Silica Chromatographic Stationary Phase by Atom Transfer Radical Polymerization and Its Chromatographic Properties

WANG Fu-Qiang, HAO Jun-Xia, DAI Xiao-Jun, GONG Bo-Lin*

2011, 32(12):  2757-2762. 

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Atom transfer radical polymerization(ATRP) of α-D-galactopyranose was conducted on the surface of 5 μm silicas at ambient temperature using 2-bromoisobutryl bromide as the initiator and CuCl/CuCl2/tris[2-(dimethylamino)ethyl]amine(Me6TREN) as the catalytic system, a novel pMAIPGal chromatographic stationary phase was obtained. The synthesized stationary phase was evaluated in detail to determine its separability, monomer synthetical process, effect of acetonitrile(ACN) and methanol on the retention of solutes. The stationary phase was characterized by means of element analysis and FTIR spectroscopy. The amount of monomer was calculated to be 0.818 mg/m2 on the surface of silica, and the stationary phase can effectively separated seven hydroxybenzene compounds and four amine compounds in reverse phase liquid chromatography(RPLC) mode. Compared with C18 column for separation of these compounds under the same chromatographic conditions, the separation efficiency was better, and the analysis time was shortened. The organic solvent content in the mobile phase has the largest influence on the retention of hydroxybenzene and amine compounds, the retention factor decreased along with increasing the organic solvent content in the mobile phase. The results show that the synthesized stationary phase has satisfactory chromatographic properties.



Preparation and Adsorption Properties of Magnetic Fe3O4@SiO2@CS Cadmium Ion-imprinted Polymer

ZHANG Ming-Lei, ZHANG Zhao-Hui*, LUO Li-Juan, YANG Xiao, LIU Yu-Nan, NIE Li-Hua

2011, 32(12):  2763-2768. 

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Magnetic Fe3O4@SiO2@CS cadmium ion-imprinted polymer(M-IIP) was prepared on the surface of silica-coated Fe3O4 nanoparticles using chitosan(CS) as functional monomer, and γ-glycidoxypropyltrimethoxysilane(GPTMS) as cross-linker. The imprinted material was characterized with scanning electron microscope(SEM) and infrared spectrum technique. The results indicated that the imprinted layer was grafted on the magnetic Fe3O4 surface, and a cubic morphological characteristic of M-IIP with edge length of 60—120 nm was observed. The selective experiment results show that the adsorption kinetics of M-IIP toward Cd(Ⅱ) is fit to pseudo first-order kinetic isotherms capacity experiment. The relative selectivity coefficient of M-IIP toward Cd(Ⅱ)/Cu(Ⅱ), Cd(Ⅱ)/Zn(Ⅱ), Cd(Ⅱ)/Pb(Ⅱ) and Cd(Ⅱ)/Hg(Ⅱ) were 2.92, 3.43, 8.97 and 9.20, respectively. The M-IIP was employed successfully to extract Cd(Ⅱ) from aqueous solution coupled with atomic absorption spectrometry(AAS) with a recovery of >98%.



Investigation of 1H NMR Profile of Vegetarian Human Urine Using ANOVA-based Multi-factor Analysis

DONG Ji-Yang, DENG Ling-Li, CHENG Kian-Kai, GRIFFIN Julian L., CHEN Zhong*

2011, 32(12):  2769-2776. 

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In this study, a technique that combined both analysis of variance(ANOVA) and partial least squares-discriminant analysis(PLS-DA) was used to compare the urine 1H NMR spectra of healthy people from a vegetarian and omnivorous population. In ANOVA/PLS-DA, the variation in data was first decomposed into different variance components that each contains a single source of variation. Each of the resulting variance components was then analyzed using PLS-DA. The experimental results showed that ANOVA/PLS-DA is efficient in disentangling the effect of diet and gender on the metabolic profile, and the method could be used to extract biologically relevant information for result interpretation.



Various Columnar Nano-structures from Self-Assembly of Triphenylene Discotic Liquid Crystalline Molecules

YANG Chun-Chang, CHEN Li, ZHONG Ke-Li, CHEN Tie, JIN Long-Yi*

2011, 32(12):  2777-2781. 

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Discotic liquid crystalline molecules, consisting of a flexible alkyl chain and a rigid block, have a strong ability to self-assemble into a variety of columnar nanostructures in the liquid crystalline phase.  In this paper, we report the synthesis and characterization of the self-assembly behavior of the three kinds of triphenylene discotic liquid crystalline molecules with various lengths of alkyl chains. Structural study of these moleculses by means of differential scanning calorimetry(DSC), polarizing optical microscopy(POM) and X-ray diffraction(XRD) revealed that the lengths of alkyl chains of triphenylene discotic liquid crystalline mo-lecules was strongly influenced the self assembly behavior in the liquid crystalline phase. The molecules containing octyl chains or dodecanyl chains self-assembled into 2D hexagonal columnar structure or 2D oblique columnar structure, respectively, in the liquid crystalline phase. While, the molecule containing hexadecyl chains did not construct ordered columnar nanostructure in the bulk state.



Catalysis of Chlorolactonization of Pentenoic Acids with Hypervalent Iodine(Ⅲ) Reagent

FANG Ying-Guo, XU Cui, ZHU Min*

2011, 32(12):  2782-2786. 

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Recently, the catalytic utilization of hypervalent iodine reagents is increasing in importance, with the growing interest in the development of environmentally benign synthetic transformations.  Halolactonization has been studied extensively, and this type of transformation serves as an important key reaction in a variety of syntheses.  However, compared with iodolactonization and bromolactonization, there are relatively few examples of chlorolactonization.  In order to improve the chlorolactonization, the cyclization of alkenoic acids under catalyst PhI was  investigated, a novel and convenient catalytic method for chlorolactonization of pentenoic acids was  developed.  In this protocol, 4-pentenoic acids reacted with lithium chloride fast under catalyst iodobenzene in combination with m-chloroperbenzoic acid as the terminal oxidant in CH2Cl2 at room temperature, which provided  five-membered chlorolactones in good yields. This method has some advantages such as mild reaction conditions, simple procedure and good yields. Furthermore, the scope of hypervalent iodine reagents in organic synthesis could be extended.



Second-order Polarizability of Y-type Triphenylamine Chromophores

LU Wei, QIAN Ying*

2011, 32(12):  2787-2794. 

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Three Y-type triphenylamine chromophores, N,N-Bis-{4-[1-(2-benzothiazolyl)-1,3-butadiene-4-yl]phenyl}aniline(BBtBPA), N,N-bis-{4-[2-(2-benzothiazolyl)vinyl]phenyl}aniline(BBtVPA), and N,N-bis-{4-[1-(3-cyano-2-dicyanomethylidene-5,5-dimethyl-2,5-dihydro-4-furyl)-1,3-butadiene-4-yl]phenyl}aniline(BCfBPA) and four dipolar ones, 1-(2-benzothiazolyl)-4-[4-(N,N-diphenyl)amino]phenyl-1,3-butadiene(BtAPB), 4-[2-(2-benzothiazolyl)vinyl]-N,N-diphenylaniline(BtVPA), 1-[(3-cyano-2-dicyanomethylidene-{5,5}-dimethyl-2,5-dihydro)-4-furyl]-4-[4-(N,N-diphenyl)-amino]-phenyl-1,3-butadiene(CfAPB) and 4-[2-(3-cyano-2-dicyanomethylidene-5,5-dimethyl-2,5-dihydro-4-furyl)vinyl]-N,N-diphenylaniline(CfVPA) were synthesized through Knoevenagel reaction, with variations in the electron acceptor substitutes and π-conjugated bridges. Absorption and fluorescence properties of these chromophores were investigated. Maxima absorption in dichloromethane were at 425 nm for BBtVPA, 443 nm for BBtBPA, and 613 nm for BCfBPA, respectively. The fluorescence maxima of BBtVPA and BBtBPA were at 516  and 558 nm, respectively. Compared with their dipolar analogues, the Y-type chromophores present about 30 nm bathochromic-shift of absorption maxima, along with slightly bathochromic-shift of fluorescence maxima. Static second-order polarizabilities β0 were obtained as 40×10-30 esu for BBtVPA, 64×10-30 esu for BBtBPA, and 238×10-30 esu for BCfBPA, respectively, by solvatochromic method based on the two-level model, while 0.9—2.8 times enhancement of β0 were observed compared with the dipolar chromophores. Besides, extension of π-conjugation and improvement of electron acceptor strength both increase the β value. Quantum chemical calculations were carried out to aid in better understanding of the structure-property relationship.



Design, Synthesis and Antifungal Activity Against Valsa Mali of the Triamino Substitued Triazines Bearing Aminopyrimidine Group

ZHAO Lian, YUAN Xiang-Guo, ZHAO Jian-Peng, CHEN Hua*, LIU Li, LI Xiao-Liu, CAO Ke-Qiang

2011, 32(12):  2795-2799. 

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In order to find novel plant fungicides targeting Valsa mali with high activity, fifteen triamino substituted 1,3,5-triazine compounds bearing 2-amino-4,6-dimethyl-5-(un) substituted pyrimidine were designed according to the antifungal characteristics of triazine and pyrimidine and the superposition principle of reinforcement of biological activity. These compounds were synthesized by amino substitution using cyanuric chloride as the starting material, and their structures were characterized and determined by 1H NMR, ESI-MS and elemental analysis. The antifungal activity against Valsa mali of the new compounds were evaluated and the results showed that a majority of the compounds have notable inhibitory activity against Valsa mali. For examples, at the concentration of 200 μg/mL, compounds 2aa, 2ba, 2ca, 2da, 3ba and 3ea have the  inhibition rate of 96.33%, 98.17%, 97.25%, 97.71%, 98.39% and 94.50%, respectively, and have the inhibition rates above 74% at the concentration of 100 μg/mL, which suggest that such triamino substituted triazine compounds have the potential applications in further development for new fungicides.



Synthesis, Crystal Structure and Insecticidal Activity of 4-(7-Methoxy-2,2-dimethyl-2,3-dihydrobenzofuran-5-yl)-N-(aryl)thiazol-2-amine

LUO Xian-Fu, HU Ai-Xi*, WANG Yu, YE Jiao, WANG Xiao-Guang, OU Xiao-Ming

2011, 32(12):  2800-2805. 

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In order to find novel insecticides with high activity, a series of 4-(7-methoxy-2,2-dimethyl-2,3-dihydrobenzofuran-5-yl)-N-(aryl)thiazol-2-amines was synthesized from 2-(2-methylallyloxy)phenol with Claisen rearrangement, cyclization of furan, etherification, Friedel-Crafts acylation, α-bromation and cyclization of thiazole. Their structures were  confirmed by mass spectrometry(MS), 1H NMR spectra and elemental analysis. The crystal structure of compound 7j was determined by X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group C2/c with a=2.21140(12) nm, b=0.87602(5) nm, c=2.13911(12) nm, β=115.5380(10)°; V=3.7391(4) nm3, Z=8, Dc=1.375 g/cm3, F(000)=1616, S=1.046, μ=0.333 mm-1, the final R1=0.0390 and wR2=0.1079. The preliminary bioassays indicated that compound 7a, 7b, 7h and 7t exhibited insecticidal activity against Aphis fabae were 95.12%, 62.60%, 57.53% and 59.06%, respectively, at 500 mg/L.



Synthesis and Antibacterial Activities of 1-(4-Substituted phenyl)-4-phenyl-5-(2-hydroxy benzyl)amino-1,2,3-triazole Derivatives

ZHAO Qian, LU Jun-Rui*, XIN Chun-Wei, BAO Xiu-Rong, GAO Hai-Yan, ZHAO Xu, LI Sha, RUI Tian-Tian

2011, 32(12):  2806-2811. 

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In order to search  for novel and high active fungicides with triazole moiety, a series of novel 1-(4-substituted phenyl)-4-phenyl-5-substituted-1,2,3-triazole derivatives was designed and synthesized by means of combining segments o-hydroxy phenyl and 1,2,3-triazole. Firstly, 1-(4-substitutedphenyl)-4-phenyl-5-(2-iminomethyl phenol)-1,2,3-triazole derivatives(3a—3e) were designed and synthesized through diazotization, azidozation, ring-closure reaction and condensation, and then were reduced by sodium borohydride to synthesize 1-(4-substituted phenyl)-4-phenyl-5-(2-hydroxy benzyl)amino-1,2,3-triazole(4a—4e). The structures of final products were determined by 1H NMR, elemental analysis and IR. The results of antibacterial activity showed that the title compounds except 3e and  4e had over 95% inhibitory rate against Monilia albican, and over 85% inhibitory rate against Escherichia coliis at  a mass concentration of  0.1 mg/L. The results suggest that the title compounds might be potential candidates for antibacterial drugs.



Isolation and Structure Characterization of Polysaccharide from Atractylodes Macrocephala Koidz

WU Le-Qin, ZHANG Jing*, SUN Run-Guang, JIANG Shao-Fen, WANG Yan-Li, DAI Jing-Jing

2011, 32(12):  2812-2816. 

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Crude polysaccharides, extracted from the stem of Atractylodes macrocephala Koidz by hot water(80 ℃), were fractionated by DEAE-52 anion exchange chromatography and purified by Sephadex G-200 gel filtration chromatography to afford a fraction, named WAM. The polysaccharide(WAM) was subjected to structural identification by a combination of chemical and instrumental analysis. The molecular weight of WAM was measured to be 3263  by high performance liquid chromatography. Gas chromatography analysis indicated that WAM composed of glucopyranose and galactopyranose in  a  molar ratio of 3.01:1.00. The infrared spectra and nuclear magnetic resonance(NMR) spectra further confirmed that the configuration of D-glucopyranose and D-galactopyranose were of β-form. On the basis of partial acid hydrolysis, periodate oxidation, Smith degradation and methylation analysis, it can be concluded  WAM had a backbone consisting of (1→3)-linked-β-D-glucopyranosyl and (1→3,6)-linked-β-D-glucopyranosyl, which was branched with a glycosyl residue, β-D-galactopyanose(1→ linked residue, at the C6 position of glucosyl along the main chain.



Expression of ACCase CT Domain in E.coli and Interaction with Herbicide

WANG Rui-Jian, ZHENG Liang-Yu*, YANG Xue-Ying, YANG Ye, WANG Xiao-Juan, CAO Shu-Gui*

2011, 32(12):  2817-2822. 

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Acetyl-CoA carboxylase(ACC) is the key enzyme in fatty acid metabolism that catalyzes the irreversible carboxylation of acetyl-CoA to produce malonyl-CoA through its two catalytic activities, biotin carboxylase(BC) and carboxyltransferase(CT). CT domain has been recognized as the critical target site of herbicide. If the soluble CT protein could be obtained, it would be beneficial for us to investigate the recognition mechanism of ACCase, further to design and develop novel herbicides. In this work, the ACCase CT domain from wheat was cloned and over expressed in E. coli in a soluble form; however the expressed protein exhibited higher hydrophobility and lower stability. In order to improve the situation, different lengths of CT genes was cloned and expressed in E. coli. The results showed that only 2325 bp gene could be expressed in a soluble form, which selected as the material to carry on the subsequent investigation; the 2109 bp gene was expressed in inclusion body state, while the 1869 bp and the 3501 bp gene could not be expressed in E. coli. The interactions of the soluble recombinant CT domain with herbicide were investigated by circular dichroism spectra(CD) and differential scanning calorimeter(DSC). The CD results showed that the spectra of CT protein were changed obviously in the presence of herbicide, indicating there was a strong interaction between the CT domain and herbicide. The DSC assay indicated that the thermal stability of recombinant CT protein was increased in the presence of herbicide. These results will provide important references for rational designing novel herbicide.



Preparation of CdS-TiO2/Rectorite Nanocomposite and Its Photocatalytic Property

XIAO Jiang-Rong, PENG Tian-You*, ZHOU Sheng-Yin, ZENG Peng

2011, 32(12):  2823-2827. 

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CdS-TiO2/rectorite nanocomposite was obtained through in-situ intercalation-exfoliation process of CdS-TiO2.  The microstructures and properties of the CdS-TiO2/rectorite were characterized by means of X-ray powder diffraction(XRD), transmission electron microscopy(TEM), Fourier transform infrared spectroscopy(FTIR), diffuse reflectance absorbance spectroscopy(DRS) and nitrogen adsorption-desorption measurement.  The adsorption and photocatalytic properties of rectorite, TiO2/rectorite and CdS-TiO2/rectorite nanocomposites were comparatively investigated by Rhodamine B(RB) as simulated organic pollutant. The experimental results show that the CdS-TiO2/rectorite nanocomposite exhibits more complicated porous structure, larger pore volume, specific surface area and more effective optical absorptivity, and therefore stronger adsorption ability and higher photocatalytic degradation activity as compared to the rectorite. The above results show a promising route for the application of the rare mineral rectroite.



Kinetics of Catalytic Hydrolysis of Phosphodiester and Plasmid DNA by the Quaternary Ammonium Salt of Chitosan with Zn(Ⅱ)

PENG Ying-Gui, ZHANG Qi, XIANG Yan*

2011, 32(12):  2828-2832. 

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The hydroxypropyl trimethyl ammonium chloride chitosan(HTACC) was synthesized by the reaction of chitosan with glycidyl trimethylammonium chloride. The kinetics of hydrolysis of bis(p-nitrophenyl)phosphate(BNPP) catalyzed by HTACC-Zn(Ⅱ) in Tris-H+ buffer was studied and analyzed. In addition, the cleavage of plasmid DNA and the molecular interaction with HTACC-Zn(Ⅱ) were also investigated. The results show that the catalyst has fine catalytic activity to the hydrolysis of phosphodiesters with a first-order rate constant of kobs＝6.7×10-6 s-1, which is 6.0×10-4 folds of its spontaneous hydrolysis. Furthermore, the catalyst can cleavage plasmid DNA(pUC19) from supercoiled form to nicked form and/or linear form effectively.



Preparation of Hydrophobic/Superhydrophobic Surface on Silicon Wafer by Reactive Ion Etching and Self-assembled Monolayers

LIAN Feng*, ZHANG Hui-Chen, ZOU He-Lin, PANG Lian-Yun

2011, 32(12):  2833-2837. 

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Micro scale pillar arrays on silicon(100) wafer were generated by reactive ion etching.  Three self-assembled monolayers(SAMs) were prepared on etched silicon wafer by self-assembled technique.  The results show that four micro pillar arrays generated by reactive ion etching possess regular structures with diameter of 5 μm, height of 10 μm and spacing of 15—45 μm.  The water contact angles of silicon wafers increase significantly after SAMs deposition, in which maximum contact angle is abtained for 1H,1H,2H,2H-perfluorodecyltrichlorosilane(FDTS) deposition, medium for 1H,1H,2H,2H-perfluorooctyltrichlorosilane(FOTS) deposition and minimum for octadecyltrichlorosilane(OTS) deposition.  The measured contact angles larger than 150°  are close to the contact angles calculated with Cassei model.  However, the measured contact angles less than 150° approach the contact angles calculated with Wenzel model.  Contact angles can be controlled by adjusting spacing of pillar array and choosing different SAMs.  Atomic force microscope(AFM) measurement show that nano scale clusters on silicon wafers appear after SAMs deposition.  Maximum contact angle of 156.0° can be acquired in surface structure with micro pillar array and nano scale SAMs.



In-situ Growth and Mechanism of the Octahedron  BaMoO4 Nanostructures

WANG Lu-De, HUANG Zai-Yin*, GUO Yun-Xiao, WANG Teng-Hui

2011, 32(12):  2838-2843. 

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RD496-2000 micro calorimeter was used to obtain thermodynamics and kinetics information of micro/nano BaMoO4 crystal in-situ growth and to explain thermodynamics and kinetics mechanism of preparation reaction about micro/nano BaMoO4. Apparent process of preparation reaction is exothermic, endexothermic and exothermic, respectively, the variational tendency of apparent rate constant k and apparent order of reaction n kept the same; however, both numerical value and velocity of variation were different. The results of calorimetry in microemulsion system and water system existed a gap, because there were collision, transfe-rence, fusion, separation and reconstitution of reverse micelle in micro emulsion, which could be analyzed by comparison.



Hydroformylation of 1-Octene over Amorphous Co-P-B Catalysts

LI Jin-Jin, MA Lan, HE De-Hua*, LI Guang-Xing*

2011, 32(12):  2844-2848. 

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Amorphous Co-P-B catalysts with different Co/P and P/B molar ratios were prepared by chemical reduction method. The catalysts were characterized with XRD, ICP-Mass and N2 adsorption-desorption isotherm. The catalysts were evaluated in the hydroformylation of 1-octene under the reaction conditions of 5.0 MPa and 120 ℃. The results showed that amorphous Co-P-B catalysts exhibited relatively high activity and selectivity in the hydroformylation of 1-octene. The molar ratios of Co/P and P/B, amorphous property and surface area affected the activity and selectivity of the Co-P-B catalysts, and the conversion and selectivity were enhanced by adding appropriate amount of P. Over the Co-P-B catalyst(Co 85.4%, P 3.3%, molar fraction), 97.2% conversion of 1-octene and 99.5% selectivity of C9-aldehyde were obtained under the reaction conditions employed in this study.



Selectively Catalytic Combustion of Acetonitrile by Transition\|metal Supported Mesoporous Molecular Sieve SBA-15

CAO Yu, CHEN Biao-Hua, ZHANG Run-Duo*

2011, 32(12):  2849-2855. 

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A series of mono-functional M/SBA-15(M=Cu, Co, Cr and Mn) catalysts was prepared via an incipient wetness impregnation, and characterized by XRD, N2 adsorption, TEM, H2-TPR and XPS as well as activity test for CH3CN+O2 reaction. Apart from the target product of N2, harmful by-products of NO, NO2, N2O, NH3 and CO were also observed during the combustion process. Among the prepared M/SBA-15 samples, Cu/SBA-15 exhibited a nearly complete conversion of CH3CN associated with a N2 selectivity around 80%, which was regarded as a promising material for the catalytic removal of cyanide-containing gas.



Electrocatalytic Performance of Carbon Supported Pt-Sn Catalyst Prepared with Direct Thermo-decomposition Method for Ethanol Oxidation

MA Juan, SUN Han-Jun, ZHAO Hong, TANG Ya-Wen, LU Tian-Hong, ZHENG Jun-Wei*

2011, 32(12):  2856-2860. 

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The Pt-Sn/C catalyst was synthesized with the direct Thermo-decomposition method using Pt(NO3)2 and SnO as the precusors. The Pt-Sn/C catalyst was characteristed with X-ray diffraction(XRD), transmission electron microscopy(TEM) and X-photoelectron spectroscopy(XPS). The electrocatalytic performance of the Pt-Sn/C catalyst was investigated with the cyclic voltammetry.  It was found that the Pt-Sn particles in the Pt-Sn/C catalyst prepared with this method possesses the shell-core structure with the Pt-Sn alloy particles as the shell and the SnOx particles as the core. The electrocatalytic performance of the Pt-Sn/C catalyst for the ethanol oxidation is better than that of the Pt/C catalyst. This preparetion method does not indroduce Cl-. Thus, the prepared catalyst needn't wash and does not induce the environmental pollution.  In addition, this preparation method is suitable for the production with the large scale.  Therefore, this preparation method is suitable for the practical application.



Optoelectrowetting on Dye Sensitized TiO2 Nanotube Film

FAN Xia*, LI Xian, TIAN Dong-Liang, ZHAI Jin*, JIANG Lei

2011, 32(12):  2861-2864. 

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Controlling of surface wetting behavior has attracted much attention because of their potential applications. In this work, the intelligent surface of N3 sensitized TiO2 nantube arrays was designed and constructed for optoelectrically cooperative conversion at low critical voltage.  Large-scale hexagonal packing TiO2 nanotube arrays on Ti substrate were fabricated by anodic oxidation method with the average length of 8  μm and inner diameter of about 120 nm.  N3 dyes(Ruthenium dye) were modified on TiO2 nanotubes surface to improve photosensitivity of the composited surface in visible light region.  Fluoroalkyl silane(FAS) was further modified on composite film to improve the surface hydrophobicity with the initial contact angle about 150°. The optoelectrically cooperative wettability conversion of modified TiO2 nanotube was obtained at critical voltage of 10 V, which was reduced by 10 V when only electrical stimulus was used.  The usage of effective N3 dye as photoelectrically sensitive layer and nanotube film with anisotropic wetting behavior resulted in this improvement, which would offer valuable information to the associated research.



Non-isothermal Kinetics for Thermal Decomposition and Recrystallization of Dickite

ZENG Yuan, HE Ming-Zhong*, ZHOU Jia, LEI Wen, FU Feng-Ying

2011, 32(12):  2865-2871. 

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The processes of the thermal decomposition and recrystallization of dickite from Fuzhou, Fujian Province have been studied in dynamic air atmosphere by a simultaneous thermal analysis instrument(thermogravimetric  analysis-derivative thermogravimetric analysis-differential scanning calorimetry, TG-DTG-DSC) and X-ray diffraction techniques.  The data of TG and DSC were used to carry out the kinetic triplet of the thermal decomposition and recrystallization,  respectively.  The Friedman method together with the non-linear regression approach was employed to determine the reaction mechanism and the kinetic parameters of the thermal decomposition.  The iterative procedure and minimum deviation were used to determine the reaction mechanism and the kinetic parameters of the recrystallization.  The results show that the thermal decomposition(dehydrate 2 molecules of water) of dickite occurs in the temperature range of 450—750 ℃ and the reaction mechanisms contains two steps continuously.  The process conforms to a random nucleation and nuclei growth model(An) and auto-catalytic model(CnC).  The recrystallization of dickite appears in the temperature range of  975—1050 ℃.  The reaction mechanism is best described by the random nucleation and nuclei growth model(An).



Simulations of Spectra of Molecular Aggregates

LI Kai, HAN Jiao, ZHANG Hou-Yu*, ABRAMAVICIUS Darius, ZHANG Han-Zhuang*

2011, 32(12):  2872-2876. 

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The absorption and emission spectra of one-dimensional linear aggregates and two-dimensional herringbone aggregates were investigated via Frenkel exciton model. The introduction of the exciton delocalization length bridges a link between spectral lineshape fuctions of molecular aggregates and single molecule. The results show that the spectra of molecular aggregates are closely dependent on the molecular alignment. The red\|shift absorption in linear J aggregates and splitting of J and H bands in herringbone aggregates are analyzed. The simulated absorption and emission spectra are in consistent with experimental results.



Theoretical Study on the Interaction between Bases and NMA by Ab initio and ABEEMσπ Methods

HUO Hong-Jie, ZHAO Dong-Xia*, YANG Zhong-Zhi*

2011, 32(12):  2877-2884. 

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DNA replication, repair and recombination must depend on the interaction with the protein. N-methylacetamide(NMA) is one of the typical units in protein. Taking NMA and the bases in DNA as the stu\|died objects, the interaction properties including geometry, charge distribution and binding energy of these NMA-base complexes were investigated in terms of the ABEEMσπ/MM method and the ab initio MP2 method. The geometry optimizations were performed at the B3LYP/6-311++G(d,p) level. The results of ABEEMσπ/MM and ab initio methods were compared. The results of ABEEMσπ/MM and ab initio methods have good agreement. The order of relative binding ability of interaction between NMA and DNA bases holds: guanine>thymine>cytosine>adenine. The parameters of ABEEMσπ/MM have good transferability. This study provides a solid foundation for the research of interaction between the protein and nucleic acid via the ABEEMσπ/MM model.



Structures and Spectroscopic Properties of Highly Efficient Luminescence Material Cationic [(C^N)2IrL]+ Complexes

ZHANG Jian-Po, JIN Li*, ZHANG Hong-Xing, BAI Fu-Quan

2011, 32(12):  2885-2890. 

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A series of iridium(Ⅲ) complexes [(C^N)2IrL]+[C^N=ppy, L=pzpy(1); C^N=dfppy, L=pzpy(2); C^N=ppy, L=pybi(3); C^N=tpy, L=acac(4); ppy=2-phenyl-pyridine, dfppy=2-(2,4-difluorophenyl)pyridine, pzpy=2-(1H-pyrazol-1-yl)pyridine, pybi=1-phenyl-2-(pyridin-2-yl)-1H-benzoimidazole, tpy=2-(4-tolyl)-pyridine, acac=acetoylacetonate] was investigated theoretically to explore their electronic structures and spectroscopic properties. Their structures in the ground and excited states were optimized at the B3LYP/LanL2DZ and CIS/LanL2DZ levels, respectively. The results indicate that the calculated bond lengths of Ir—N, Ir—C, and Ir—O in the ground state agree well with the corresponding experimental results. Upon excitation, the bond lengths of Ir—N and Ir—C lengthen by 0.0003—0.003 nm and that of Ir—O shortens by ca. 0.0012 nm compared with those of ground states. At the time-dependent density functional theory(TD-DFT) level with the polarized continuum model(PCM), complexes 1—4give rise to lowestying absorptions at 398 nm(1), 370 nm(2), 419 nm(3), and 437 nm(4) and phosphorescent emissions at 511 nm(1), 457 nm(2), 602 nm(3), and 479 nm(4), respectively. The transitions of complexes 1, 2 and 4 are attributed to d(Ir)+π(C^N)→π*(C^N) charge transfer, whereas those of complex 3 are related to d(Ir)+π(C^N)]→π*(pybi). It is shown that the emissions are significantly dominated by the metal participating in the frontier molecular orbitals and affected by the L ligands.



Effects of collagen liquid crystalline films on cell culture

TANG Min-Jian, DING Shan, MIN Xiang, JIAO Yan-Peng, ZHOU Chang-Ren*, LI Hong

2011, 32(12):  2891-2895. 

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A series of biomimetic collagen films was prepared. The texture and topological structure of collagen films were studied by polarizing optical microscopy(POM), scanning electron microscopy(SEM) and atomic force microscopy(AFM). The relationship between collagen membranes and 3T3 cells was studied by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide(MTT) method and cytoskeleton fluorescence staining. The results show that the collagen liquid crystal(LC) membranes present continuously twisting orientations in cholesteric phases characterized by typical series of arced patterns. Compared with the non-LC membranes, LC membranes not only could promote the cell's adhesion and proliferation, but also the LC topological structure had a contact guide effect to 3T3 cells.



Effect of Silica Nanoparticles on the Morphology of Immiscible PIB/PDMS Blends in Confined Shear Flow

PENG Xiao-Juan, HUANG Ya-Jiang*, HE Yu-Song, LUO Yong, YANG Qi, LI Guang\|Xian

2011, 32(12):  2896-2901. 

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The morphology development in immiscible polymer blends under confined shear flow(such as in the field of micro-processing) usually differs significantly to that observed in bulk conditions. In this work, the effect of silica nanoparticles with different surface properties on the morphology development of immiscible polyisobutylene(PIB)/polydimethylsiloxane(PDMS)(10:90) blends under confined shear flow was investigated. The confined environment was created by an optical-shear cell united system. It was found that the addition of only a very small amount(0.2%) of hydrophobic SiO2 nanoparticles could suppress the coalescence of dispersed droplets effectively and thus decreased the confinement degree of droplets. As a result, the formation of the superstructures(such as pearl necklaces and strings), as presented in the pure PIB/PDMS blends, were prevented and the blends displayed a near bulk behavior. On the contrary, the blends with the addition of small amount of hydrophilic SiO2 nanoparticles still formed superstructures of dispersed droplets under shear flow. Bulk behavior of dispersed phase could only be obtained with higher concentration of the hydrophilic SiO2 nanoparticles and under higher shear rate.



Preparation of Cobalt(Ⅱ) Ion Imprinted Silica Gel Sorbents by Surface Imprinting Technique and Its Adsorption Properties

FAN Hong-Tao, SUI Dian-Peng, ZHAO Li-Xing, REN Ze-Yan, YUAN Zi-Yun, ZHOU Qin, SUN Ting*

2011, 32(12):  2902-2907. 

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A Co(Ⅱ) ion imprinted silica gel sorbent was prepared by surface imprinting technique using Co(Ⅱ) as the template, 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane as the functional monomer, silica gel as the support, and epichlorohydrin as the crosslinking agent, and was characterized by Fourier transform infrared(FTIR) spectra, scanning electron microscopy(SEM) and thermogravimetric analysis-differential thermal analysis(TG-DTA). The adsorption property and selective recognition ability of Co(Ⅱ) ion imprinted silica gel sorbent were studied by equilibrium\|adsorption method. The results showed that the maximum static adsorption capacity of ion imprinted and non-imprinted silica gel sorbent were 35.2 and 6.5 mg/g, respectively. The experimental data followed the Langmuir adsorption model. The adsorption equilibrium could be reached in 20 min. There was no influence of pH values on adsorption capacity of ion imprinted silica gel sorbent in the range of 3.9—7.8. Co(Ⅱ) ion imprinted silica gel sorbent could be used repeatedly and indicated high selectivitys even in the presence of the other metal ions.



Isothermal Crystallization Kinetics of Thermoplastic Polyimide and Poly(ether ether ketone) Blends

GUO Lai-Hui, FANG Xing-Zhong*, WANG Gui-Bin, WU Zhong-Wen

2011, 32(12):  2908-2915. 

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Thermoplastic polyimide(TPI) and poly(ether ether ketone)(PEEK) blends were prepared by melt blending and the isothermal crystallization kinetics of the blends was investigated by differential scanning calorimetry(DSC). Avrami equation and Hoffman-Lauritzen equation were used to analyse the isothermal crystallization kinetics, folding-surface free energy(σe) and the work of chain folding(q), respectively. The results showed that the rate of crystallization of PEEK decreased, while activation energy of crystallization, σe and q increased when TPI was added. But there was no linear relationships between the changes of these values and the content of TPI. A possible explanation was given by the investigation of the miscibility and surface morphology of the blends.



Preparation of Nucleus-targeting Polyethyleneimine-dexamethasone Conjugates and Their Application for Gene Delivery

FAN Ying, YAO Jing*, ZHOU Jian-Ping*

2011, 32(12):  2916-2622. 

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The study aimed to develop polyethyleneimine-dexamethasone(PEI-Dex) conjugates for the nucleus-targeting gene delivery by amidation reaction. The results showed that the PEI-Dex could effectively condense DNA and form the PEI-Dex/DNA complex. The size of the complex at the optimal N/P ratio was (162±1.90) nm and zeta potential was (12.8±0.11) mV, which could facilitate the gene transfection. Moreover, it exhibited much higher transfection efficiency compared with the PEI 1800/DNA complex due to efficient nuclear translocation and low cytotoxicity. In conclusion, PEI-Dex should be a promising non-viral gene vector.



Preparation of the Core-Shell Silicone-acrylic Latex and Its Film Formation Mechanism

MU Yuan-Chun, LI Xiao-Chen, QIU Teng, HE Li-Fan, ZHANG Sheng-Wen, LI Xiao-Yu*

2011, 32(12):  2923-2928. 

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We describe a method via transition emulsion polymerization for the synthesis of phase-separated polymer latex with multilayer core-shell(MLCS) morphology. We used four-step process emulsion polymerization for the preparation of MLCS latex. The acrylic esters were employed as the main monomers for the core and the shell of the latex, which was copolymerized by vinyl siloxane monomer. The transmission electron micrograph(TEM) and dynamic light scattering(DLS) methods were applied to characterize the MLCS emulsion. The core-shell silicone-acrylic structure was clearly shown in the TEM image, and the structure of the MLCS latex particles which contained three glass transition temperatures was further proved by the stochastic temperature-modulated-differential scanning calorimetry(TOPEM-DSC). The DLS analysis show that the average diameter and shells thickness of MLCS latex are corresponding to the TEM image. The whole process of the film formation was carried out using the Horus film formation analyzer. On this basis, the water-based coating with various auxiliary agents was prepared. The film performances are excellent, such as hardness, acetone resistance, water resistance, alcohol resistance, and indentation resistance.