Table of Content

10 June 2012, Volume 33 Issue 06

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Content

Cover and Content of Chemical Journal of Chinese Universities Vol.33 No.6(2012)

2012, 33(06):  0-0. 

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Letter

Synthesis of Sulfonated Fluorenyl-containing PEEKK and Its AMPH-POSS Hybrid Membranes

LI Long, LIU Bai-Jun, LIU Si-Yuan, JIANG Zhen-Hua

2012, 33(06):  1121-1123.  doi:10.3969/j.issn.0251-0790.2012.06.001

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Fluorenyl-containing sulfonated poly(ether ether ketone ketone) was synthesized through a post-sulfonation method as the matrix, and AMPH-POSS was selected as filler to form acid-base enhanced proton exchange membranes by solution casting. The microstructure and some basic properties were investigated. The filler was well dispersed in the polymer matrix. The hybrid membranes exhibited improved swelling stability, selectivity and methanol permerbilities.



Article: Inorganic Chemistry

Quick Fabrication of Continuous and Compact Silicalite-1 Membrane on Stainless Steel Net

ZHANG Cong, YAN Wen-Fu, YU Ji-Hong, XU Ru-Ren

2012, 33(06):  1124-1129.  doi:10.3969/j.issn.0251-0790.2012.06.002

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A new method for quick fabrication of continuous and compact silicalite-1(Si-MFI) membrane on stainless steel net was developed. The method consists of pre-treatment of substrate of stainless steel net with silica solution containing polyethylene oxide(PEO) polymer and a secondary growth process. The continuous and compact Si-MFI membranes were obtained within 12 h. The membrane was further characterized by scanning electron microscopy(SEM) and X-ray diffraction(XRD) analyses. SEM analyses show that the membrane is continuous and highly compact. XRD analyses suggest that the micro-crystals embedded in the membrane are well crystallized. The permeance and separation performance of the Si-MFI membrane were exa-mined with a gas-separation setup combining a gas chromatography. The results show that the Si-MFI membrane has an excellent permeance and separation performance for CO₂ and N₂.



Synthesis, Electrochemical and Spectral Properties of Novel meso-Chlorophenyl Substituted Free-base Corroles

OU Zhong-Ping, ZHU Jia-Li, LIN Wen-Sheng, FANG Yuan-Yuan, LU Gui-Fen

2012, 33(06):  1130-1137.  doi:10.3969/j.issn.0251-0790.2012.06.003

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Two novel free-base chloro-substituted triphenylcorroles 5,10,15-tri-(4-chlorophenyl)corrole [(ClPh)₃CorH₃] and 5,10,15-tri(2,4-dichlorophenyl)corrole [(Cl₂Ph)₃CorH₃] were synthesized and characte-rized by UV-Vis, IR, ¹H NMR and mass spectroscopy. The electrochemical and spectroscopic properties of the corroles were examined in dichloromethane and N,N'-dimethylformamide containing 0.1 mol/L TBAP. The effect of solvents and substituents on UV-Vis spectra and redox potentials as well as the electron transfer process of the corroles were discussed. Based on the results of electrochemistry, spectroelectrochemistry and electron spin resonance(ESR) measurements overall reduction/oxidation mechanisms of the corroles were proposed.



Morphology and Crystallization Character of Calcium Carbonate in Scaled Sample Formed During Alkaline-surfactant-polymer(ASP) Flooding in Daqing Oilfield

CHENG Jie-Cheng, ZHOU Wan-Fu, WANG Qing-Guo, CHENG Tie-Xin, ZHOU Guang-Dong

2012, 33(06):  1138-1142.  doi:10.3969/j.issn.0251-0790.2012.06.004

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Alkaline surfactant polymer(ASP) flooding could improve oil recovery considerably, however, scales have also been found in the injection and production systems simultaneously. Investigation shows that CaCO\-3 of scaled sample has different morphological characters such as stick and sphere, and sliver crystallographic character. Due to the existence of partial hydrolyzed polyacrylamide(HPAM), the critical micelle concentration for the heavy alkyl benzene sulfonate surfactant(HABS) decreases, i.e., micellization of HABS could be accelerated. On the other hand, the addition of HABS accelerates negative electric attract ability of HPAM and makes the steely properties of the chains stronger. Micelle and HPAM could act as template, which leads to the formation of CaCO\-3 in the scaled sample with different morphologies. In addition, the coexistence of HPAM and surfactant does not change the character of sliver CaCO\-3 in the scaled sample. This study will be helpful for deep analysis on ASP flooding scaling mechanism, scale remover and inhibitor, and thereby increase the service life of ASP flooding well, scale up and popularize the ASP flooding.



Syntheses, Structures and Spectra Studies of Like-scorpionate Copper Complexes

WANG Xin-Yu, XING Na, SONG Ge, LI Zhen, BAI Feng-Ying, XING Yong-Heng

2012, 33(06):  1143-1150.  doi:10.3969/j.issn.0251-0790.2012.06.005

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A planar tridentate pyrazole-triazine like-scorpionate compound, 2,4-bis(3,5-dimethylpyrazol-1-yl)-6-diethylamino-1,3,5-triazine(bpz*eaT) and its two complexes ₂?(CuCl₄)(1) and Cu_1.5Cl₃(bpz*eaT)(2) were synthesized in the organic solvent system. The complexes were characterized by elemental analysis, IR, UV and fluorescence spectra, thermogravimetric analysis, X-ray powder and X-ray single crystal diffraction technology and the structural characters of the two complexes were analyzed. The structural analysis shows that bpz*eaT is in tridentate chelated coordination mode and the coordination numbers of the center metal coppers in complexes 1 and 2 are all five, exhibiting a slightly distorted pentahedron configuration. Furthermore, the stabilities and charge distribution of the complexes were calcula-ted by quantum chemistry.)



Synthesis and Properties on Promoting DNA Condensation of Polybenzimidazole Mn(Ⅱ) Complexes

HUANG Xue-Ying, MENG Xiang-Gao, ZHANG Yan, WANG Li, LIU Chang-Lin

2012, 33(06):  1151-1157.  doi:10.3969/j.issn.0251-0790.2012.06.006

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Complexes [Mn(DTPB)Ac]Ac·8H₂O(1) and [Mn₂(DTPB)(NO₃)₂(H₂O)₂][Mn₂(DTPB)·(NO₃)₂·(H₂O)·(CH₃OH)](NO₃)₄·5CH₃OH·H₂O(2) were synthesized via 1,1,4,7,7-pentakis(1H-benzimidazol-2-ylmethyl)-1,4,7-triazaheptane(DTPB) as the main ligand and characterized by X-ray diffraction. The interaction between complexes 1 or 2 and DNA, examined by UV-Vis absorption spectra and viscosity experiments, indicated that the two Mn(Ⅱ) complexes have strong affinity for DNA. The interaction mechanism of the complexes with DNA was discussed. These Mn(Ⅱ) complexes can promote DNA condensation under neutral conditions, as illustrated by gelose gel electrophoresis and right angle light scattering(RALS). The morphologies of the DNA condensates were observed by transmission electron microscopy(TEM).



Analytical Chemistry

Detection of Cysteine in Aqueous Solution Based on Indicator Displacement by Ultraviolet-Visible and Colorimetric Methods

LI Yong-Ling, ZHANG Jian-Gang, WEI Yan-Li, CHENG Fang-Qin

2012, 33(06):  1158-1161.  doi:10.3969/j.issn.0251-0790.2012.06.007

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Through ultraviolet-visible(UV-Vis) spectra, a strategy for the determination of cysteine(Cys) was established by simply assembling copper(Ⅱ) and 4-(2-pyridylazo)-resorcinol(PAR) in a molar ratio of 1: 1 in aqueous solution. Cys could be detected in 10 mmol/L 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid(HEPES) buffer(pH=7.0) system containing copper(Ⅱ)-PAR due to coordination competition. The Cu²⁺-PAR ensemble was highly selective for Cys without interference from other amino acids. From the UV-Vis absorbance value changes of Cu²⁺-PAR and Cu²⁺-PAR-Cys, the optimal coordinated ratio of PAR: Cu²⁺ was found to be 1: 1 and Cu²⁺:Cys was 1: 3. It is worthy mentioned that within the concentration range of 0—240 μmol/L in aqueous solution, the measurement of Cys conformed well with linear law, with an average coefficient of light extinction of 7519 L/(mol·cm) and a correlation coefficient of 0.9982. The whole recognition process for Cys gave rise to a rapid visual color change from pink to yellow which can be observed simulta-neously with naked eye.



Electrogenerated Chemiluminescence Biosensor Based on Ru(bpy)₃²⁺ Doped Mesoporous Silica Nanoparticles

WANG Yong-Hong, HE Xiao-Xiao, WANG Ke-Min, SU Jing, CHEN Zhi-Feng, YAN Gen-Ping

2012, 33(06):  1162-1166.  doi:10.3969/j.issn.0251-0790.2012.06.008

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A novel electrogenerated chemiluminescence(ECL) sensor based on Ru(bpy)₃²⁺-doped MCM-41 mesoporous silica nanoparticles(MSN) was developed. The Ru(bpy)₃²⁺ was first loaded into the sulfhydryl modified MSN through the electrostatic absorption. Then the Ru(bpy)₃²⁺-doped MSN was immobilized onto the surface of Au electrode by Au-S interaction. The properties of electrochemistry and electrogenerated chemiluminescence(ECL) were also investigated. The amino structure of melamine is similar to tripropylamine, so we attempted to branch out the application of MCM-41 into the detection of melamine, the ECL sensor provided a new assay for the detection of melamine. Furthermore, the research provided a new approach for the immobilization of Ru(bpy)₃²⁺ onto the electrode surface.



Independent Adjustable Ion Source for Accurate Mass Determination

MA Li-Po, WANG Guang-Hui, XIN Bin, CHEN Yi

2012, 33(06):  1167-1171.  doi:10.3969/j.issn.0251-0790.2012.06.009

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Ambient electrospray guns were fabricated. They worked independently and could easily be set at any ambient inlet of a mass spectrometer(MS) such as Quadrupole-Time of Flight(Q-TOF) MS. By adjusting the distance and/or angle of their nozzles to the inlet, the signal intensity was dynamically regulated without any change of sample concentration and stop of the equipment. Using two of such guns, sample and calibrants were sprayed, ionized and introduced into the mass spectrometry separately but simultaneously. The peak ratio of sample to calibriant was dynamically adjusted to about 1: 1 and high accurate molecular mass was measured, with an error of -2.7?10^-6 which was -2.9?10^-6 by common internal calibrating determination. The method has been validated by a long time(>20 months) measure of different samples(>100) from various laboratories. The overall mass errors were kept within ?5?10^-6. It can be concluded that the method is facile, flexible, time- and cost-effective, and universally applicable.



Redox of Flavonoids with Chlorauric Acid and Its Analytical Application

WANG Hui-Juan, LI Chun-Mei, LIU Yue, LI Yuan-Fang

2012, 33(06):  1172-1176.  doi:10.3969/j.issn.0251-0790.2012.06.010

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Four flavonoids including genistein, luteolin, daidzein and naringenin can reduce HAuCl₄ to form gold nanoparticles in different acidity. There are good linear correlations between the signal of plasmon resonance absorption of gold nanoparticles and the concentration of four flavonoids. Thus, we developed a method to detect these four flavonoids respectively. By analyzing the molecular structure and calculating the electron cloud density distribution of the atoms using Materials-studio 4.0, we found that suitable pH for the reaction of different flavonoids and HAuCl₄ was related to the number of phenolic hydroxyl group of flavonoid and electron cloud density distribution of alkaline oxygen atoms.



Determination of Transferrin in Human Serum Samples Using Chicken Egg Yolk Antibodies(IgY) by Surface Plasmon Resonance

WANG Chun-Yu, FENG Feng, BAI Yun-Feng, CHEN Ze-Zhong, TIAN Mao-Zhong, QIU Jian-Ding, NI Yong-Nian

2012, 33(06):  1177-1181.  doi:10.3969/j.issn.0251-0790.2012.06.011

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Chicken egg yolk antibodies(IgY) instead of traditional mammalian antibodies were immobilized to a sensor chip CM5 for the detection of transferrin in human serum by surface plasmon resonance(SPR). The conditions for immobilizing chicken anti-human transferring antibodies and regeneration were studied. Chicken egg yolk antibodies were immobilized under the condition of a flow rate of 5 μL/min, pH=4.0 and the concentration of 100 μg/mL. The good linear range was obtained over 50—500 ng/mL, the detection limit was 39.56 ng/mL. The determination of transferrin in human serum showed good reproduction and precision, intra-day CV was below 5%, and inter-day CV was below 8%, average recoveries ranged from 86.22% to 94.51%.



Reversible Control of Fluorescence Based on the Interaction Among CdTe QDs, CHA and AngⅠ

WANG Xiao-Dan, YIN Peng-Fei, GONG Hui-Ping, LI Ping-Ping, LIU Zheng-Qing, HE You-Qiu

2012, 33(06):  1182-1187.  doi:10.3969/j.issn.0251-0790.2012.06.012

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Using mercaptopropinic acid(MPA) as the stabilizer, CdTe quantum dots(QDs) were synthesized in aqueous solution. Their particle sizes and morphology were characterized by transmission electron microscope(TEM) and atomic force microscope(AFM). Chlorogenic acid(CHA) can quench the fluorescence of CdTe QDs effectively, and the quenching values of fluorescence were proportional to the concentration of CHA in a certain concentration range. The interaction between CdTe QDs and CHA was investigated via fluorescence spectrometry, UV-Vis absorption spectrometry and Fourier transform infrared spectrometry. The preliminary judgement of the quenching mechanism is dynamic quenching, and a theoretical basis of fluorescent spectrometry methods for the determination of trace amounts of CHA was provided. When angiotensinⅠhuman acetate salt hydrate(AngⅠ) was added into the CdTe QDs-CHA system, the fluorescence of CdTe QDs was recovered in a certain concentration range, thus reversible control of fluorescence of the QDs was realized. The process of fluorescent quenching and recovering of CdTe QDs has a guiding significance for the design of fluorescence sensor and the study of mechanism of reversible control of fluorescence.



GC/TOF-MS-based Analytical Method of Endogenous Metabolites for Mouse Serum

WU Sheng-Ming, FENG Bo, CHENG Jian-Hua, LI Hai-Jing, FANG Jun-Jian, YAN Xian-Zhong, WEI Lai, DONG Fang-Ting

2012, 33(06):  1188-1194.  doi:10.3969/j.issn.0251-0790.2012.06.013

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A gas chromatography/time of flight-mass spectrometer(GC/TOF-MS) method of metabonomic analysis for small mouse serum was established. With optimizing derivatization, 269 peaks of GC/TOF-MS chromatogram were detected. Among them, 46 peaks with the similarity over 800 were identified for endogenous metabolites. 18 endogenous metabolites were selected randomly to evaluate the precision and stability of the method, and 14 mixture standard of amino acids were selected for quantitative analysis. The results showed that linearities of the 14 mixture standards were good over the range of 2.78—113.20 ng/μL, precision for intra-day and inter-day tests were satisfying, and the precision values were all below 15% for 18 endogenous metabolites. Since trimethyl-silyl(TMS) derivatization of monosaccharides often results in the formation of multiple peaks, oximation can resolve the problem smoothly. The results suggest that the method could be usefully applied to metabolomic studies, by data processing, biological markers can be identified and a new way can be presented for disease diagnosis.



Ligand Effects on Selective Interaction of CdTe Quantum Dots with BSA

WANG Shan-Shan, WANG Xue-Ting, GUO Ming-Ming, YU Jun-Sheng

2012, 33(06):  1195-1204.  doi:10.3969/j.issn.0251-0790.2012.06.014

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Five water-soluble CdTe quantum dots(QDs) were synthesized using thioglycolic acid(TGA), 3-mercaptopropionic acid(MPA), 1-thioglycerol(TG), L-cysteine(L-cys) and glutathione(GSH) as stabili-zers, respectively. The interaction of CdTe QDs with bovine serum albumin(BSA) was studied by UV-Vis absorption and photoluminescence spectroscopy. Experimental results demonstrated that fluorescence of BSA could be markedly quenched by all these five CdTe QDs in Tris-HCl buffer solution(pH=7.40). The quenching ability of CdTe QDs to BSA is as GSH>L-cys>TGA>TG>MPA in the order of ligands. However, when BSA was added into CdTe QDs solution, five CdTe QDs exhibited apparently selective responses to BSA. As the concentration of BSA increased, fluorescence intensity of CdTe QDs capped by TGA and MPA were both significantly enhanced firstly, then declined sharply. Under the same experimental conditions, fluore-scence intensity of L-cys-capped CdTe QDs was significantly quenched by BSA, and that of TG-capped CdTe QDs was only slightly quenched by BSA. While almost no change of GSH-capped QDs fluorescence was observed in the presence of BSA. These results indicated that ligand molecular structure of CdTe QDs played an important role in the interaction between BSA and CdTe QDs. Time-resolved luminescence dynamics suggested that the ground state complex of BSA and CdTe QDs could form by electrostatic interaction. Possible interaction mechanism of BSA with CdTe QDs was proposed based on the molecular structure of ligands.



Organic Chemistry

Influence of Configuration on Photoinduced Electron-transfer Mechanism in Sulfonyl Amidine Linked Porphyrin-fullerene Dyad

HE Lin, CHEN Chen, LI Fei, ZHU Yi-Zhou, ZHENG Jian-Yu

2012, 33(06):  1205-1213.  doi:10.3969/j.issn.0251-0790.2012.06.015

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A novel sulfonyl amidine linked porphyrin-fullerene dyad ZnP-H-C₆₀ was facilely synthesized via a three components one-pot coupling reaction. There are two isomers(Z- and E-) in the dyad solution in low-polarity solvents, such as chloroform and toluene. We found that the photoinduced electron-transfer(PET) process could occur in two isomers, but the electron-transfer mechanism was different from each other. The electron transfer process was mediated by the intramolecular hydrogen-bond in (Z-)ZnP-H-C₆₀; and in (E-)ZnP-H-C₆₀, the porphyrin-fullerene exciplex was the precursor of the charge separation(CS) state due to the closer distance between porphyrin and fullerene entities.



Preparation of β-Cyclodextrin Functionalized Graphene and Enhancement of the Thermal Stability

ZHANG Shu-Peng, SONG Hai-Ou

2012, 33(06):  1214-1219.  doi:10.3969/j.issn.0251-0790.2012.06.016

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Two β-cyclodextrin modified graphene nanomaterials were prepared by employing two synthetic strategies. Their structures and performances were characterized by Fourier transform infrared spectroscopy(FTIR), X-ray diffraction(XRD), transmission electron microscope(TEM), scanning electron microscopy(SEM) and thermogravimetric analysis(TGA). The results showed that their dispersion behaviors would be influenced by the structures of nanomaterials. GO-CDs and GO-TDI-CDs can be dispersible in DMF, DMSO and ethylene glycol better, which is similar to GO. At the same time, introduction of CDs improves significan-tly the thermal stability of nanomaterials, which suggest their great potential as the flame retardants industry.



Cytotoxic Labdane-type Diterpenes and Diterpene Derivative from Hedychium villosum

ZHAO Qing, ZOU Cheng, YU Qin, ZHAO Sheng-Ding, HE Hong-Ping, HAO Xiao-Jiang

2012, 33(06):  1220-1225.  doi:10.3969/j.issn.0251-0790.2012.06.017

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Research on active components from rhizomes of Hedychium genus has led to isolation of some diterpenes with significant cytotoxic activities against Chinese hamster V-79 cells, KB cells, K562 cells, A549 cells, etc.. Hedychium villosum Wall. is a perennial rhizomatous herb distributed in China and partially in Southeast Asia, which is used in the treatment of pain and inflammation. A new labdane-type diterpene(1), together with a known one(3), were isolated from Hedychium villosum. The new diterpene was named as villosumcoronarin, which partially isomerized to its epimer 1' in solution, e.g., chloroform or methanol. The gross structures of compounds 1 and 1' were elucidated on the basis of MS, IR, ¹H NMR, ¹³C-DEPT NMR, ¹H-¹H COSY and HMBC. The relative configuration was determined by ¹H NMR, ROESY and computational methods. Compound 1 was identified as(11S, 15R)-11-hydroxy-8(17), 12(E)-labdadien-15,16-dial 11,15-hemiacetal. The known compound 1 was oxidized by Jones reagent to get diterpene derivative 1. Bioassays revealed that compound 1 had strong cytotoxic activity against HL-60 and SMMC-7721 cells with IC₅₀ values of 0.74 and 4.48 μmol/L, respectively, the activities were stronger than the positive control, cis-diaminedichloroplatinum(DDP). Compound 1 also showed significant activities against HL-60 and SMMC-7721 cells with IC₅₀ values of 3.15 and 9.57 mmol/L, respectively.



Synthesis and Biological Evaluation of Nicotinamide Adenine Dinucleotides Analogues as Inhibitors of CD38

CHEN Zhe, KWONG Anna Ka-Yee, YANG Zhen-Jun, ZHANG Liang-Ren, LEE Hon Cheung, ZHANG Li-He

2012, 33(06):  1226-1232.  doi:10.3969/j.issn.0251-0790.2012.06.018

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CD38 is the main mammalian ADP-ribosyl cyclase and a signaling enzyme responsible for catalyzing the synthesis of Ca²⁺-messengers and plays a critical role in a wide range of physiological functions. It is of great interest to develop specific and generally applicable inhibitors of CD38. Fluoro-substituted nicotina-mide adenine dinucleotides(NAD), such as ara-F NMN and ara-F NAD, are catalysis-dependent inhibitors of CD38 and are often used as probes for investigating the function of CD38. For understanding the effect of fluoro-substitution on activity in more detail and discovery of active inhibitors of CD38, compounds 2a—2c were synthesized and their inhibition against the hydrolysis activities of CD38 were evaluated. The syntheses were performed by starting from the corresponding fluoro-substituted sugar, then followed by coupling with nicoti-namide, regio-selective 5'-phosphorylation and condensation with adenosine monophosphate, successively. All target compounds were purified by HPLC and characterized by NMR and HRMS. Two compounds showed strong inhibitions, especially 2'-deoxy-2'-fluororibonofuranosyl which gave activity with IC₅₀ of 0.056 μmol/L and was two orders of magnitude higher than positive control ara-F NAD. The results also showed that the activity was greatly affected by the number and the position of fluorine atom on the sugar ring, as well as the configuration of the inhibitors. The detailed biological investigation and structure-activity relationship are underway.



Analysis of N-Glycans Profiling from HeLa Cells by Matrix-assisted Laser Desorption/Ionization Time-of-flight Mass Spectrometry

WANG Pei-Pei, YU Guang-Li, JIAO Guang-Ling, ZHAO Xia, LI Jing, CHAI Wen-Gang

2012, 33(06):  1233-1238.  doi:10.3969/j.issn.0251-0790.2012.06.019

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The structure of N-glycans on cell surface was abnormal in the process of cancer, which was closely related to the invasion and metastasis of tumors. Total glycopeptides were obtained from trace HeLa cells(10⁷) after cell lyses, reduction and acetamidation, trypsin digestion and Oasis-HLB cartridge purification. N-glycans were released by PNGase F digestion and purified by a Sep-Pak C₁₈ cartridge. The structural of N-glycans profiling was first analyzed by positive-ion matrix-assisted laser desorption/ionization time-of-flight mass spectrometry(MALDI-TOF MS) after permethylation. The 34 types of N-glycans obtained from HeLa cell included both high-mannose and complex(bi-, tri-, tetra- and penta-antennary) types, some of the latter containing bisecting and Lewis determinants, which were relevant to tumor metastasis in same way. The MALDI-TOF MS technology was suitable for rapid analysis of N-glycans profiling on cancer cell surface in trace amount, in order to find new glycans-makers and more foundation for prevention and diagnosis in early stage of tumors.



Synthesis of Two Anion Receptors of 1H-Imidazo[4,5-f][1,10]phenanthroline Derivatives and Their Recognition Properties

CHEN Hua-Mei, YUE Fan, LIN Hai, LIN Hua-Kuan

2012, 33(06):  1239-1244.  doi:10.3969/j.issn.0251-0790.2012.06.020

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Anion play important roles in a wide range of chemical, biological and environmental processes. So anion binding and sensing became an active research field in supramolecular chemistry with potential applications in biomedical and environmental monitoring, anion exchange as well as anion transport. Artificial neutral receptors for anions are designed and synthesized in which color metric sensors are paid a good deal of attention for they could efficiently change their photo physical properties in the presence of anions. Imidazole and phenol are recently used in the design of neutral receptors for anions due to their ability to act as H-bond donors. Two anion receptors of 1H-imidazo[4,5-f][1,10]phenanthroline derivatives, 2-(2-hydroxyphenyl)-1H-imidazo[4,5-f][1,10]phenan-throline(1) and 2-(2-hydroxy-5-bromophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline(2) were designed and synthesized, and the structure of compound 2 was confirmed by single crystal X-ray diffraction analysis. Anion sensing and the mechanism studies were carried out by UV-Vis spectrophotometric titration and ¹H NMR titration. The receptors exhibited sensing towards CH₃COO^-, F^- and H₂PO₄^- with color of the solution changed from pale yellow to yellow, and weakly sensing towards Cl^- with inconspicuous response towards Br^- and I^- in DMSO. The receptors formed hydrogen bond supramolecular with anions F^-, H₂PO₄^- and CH₃COO^- as 1: 1 within[receptor]/[anion]=1. As flowed with the molar ratio exceeded 1, the proton of 1H-imidazo deprotoned and linked with the anion. The receptors formed hydrogen bond supramolecular with Cl^-.



Biological Chemistry

Influences of Ionic Liquids on Catalytic Performances of Papain

HOU Xue-Dan, LOU Wen-Yong, YAN Li-Qiang, ZONG Min-Hua

2012, 33(06):  1245-1251.  doi:10.3969/j.issn.0251-0790.2012.06.021

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A series of ionic liquids(ILs) based on 1-butyl-3-methylimidazolium([BMIm]), N-ethylpyridi-nium(EPy) and tetraethylammonium([NEt₄]) cations with various kinds of anions(H₂PO₄^-, ClO₄^-, HSO₄^-, CH₃COO^-, Cl^-, Br^-, NO₃^-, SCN^-, BF₄^-, PF₆^-) was examined for their influences on papain-mediated hydrolysis of N-benzoyl-L-arginine ethyl ester. By assaying the hydrolysis activity and thermodynamics deactivation parameters of papain in all these IL-containing systems, it was found that there was no correlation between the enzymatic activity or thermostability and the ILs kosmotropicity. Thus, the Hofmeister effect was not regarded as a good explanation for remarkable effects of ILs on catalytic performance of papain. In the case of BF₄^--based ILs combined with various cations, only [BMIm][BF₄] enhanced the hydrolysis activity of papain, and other ILs lowered the enzymatic activity. However, most of all the tested ILs improved the enzymatic thermostability apart from the strong acidic one -[HOOCMMIm][BF₄]. Among all the examined ILs, the BF₄^-- or PF₆^--based ILs markedly enhanced the activity or thermostability of papain. The enzyme exhibited the highest hydrolysis activity with [BMIm][PF₆], and the best thermostability with [HOEtMIm][BF₄].



Effects of Net Charge on Biological Activities of Alpha-helical Anticancer Peptides

HUANG Yi-Bing, ZHAI Nai-Cui, GAO Gui, CHEN Yu-Xin

2012, 33(06):  1252-1258.  doi:10.3969/j.issn.0251-0790.2012.06.022

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Owing to the low possibility of induction of resistance, amphipathic α-helical anticancer peptides whose sole target is the biomembrane show their promising potentials in cancer treatments. Obtained in the previous study, an amphipathic α-helical anticancer peptide A12L/A20L(Peptide P) with significant anticancer activity was utilized as the framework to systematically design a series of peptide analogs with different net charges by amino acid substitutions on the polar face, and to study the effects of net charge on biological activities of cationic anticancer peptides. The results showed that there was an obvious net charge threshold among peptide analogs, that was the net charge of +7 to +8 and the number of electrostatic repulsion of 3—5. Increases or decreases of net charges beyond the threshold value resulted in a dramatic reduction in both anticancer activity and therapeutic index. The alteration on net charges of peptides exhibited weak effect on hemolytic activity(maximum 2-fold) but significant influence on anticancer activity and therapeutic index(maximum 10-fold), respectively. Compared with the neutral membrane of human normal cells, the negatively charged membrane of cancer cells was much more sensitive to net charge alteration of the anticancer peptide. The amphipathic α-helical anticancer peptides showed good specificity between cancer cells and human normal cells, which might play a crucial role in making further improvement in target selectivity and designing anticancer peptide agents as therapeutics with higher efficacy and lower toxicity.



Physical Chemistry

Theoretical Investigation of Structure and Properties of Ge@C₈₂

HONG Bo, JIN Dong-Ri, LI Yun, MA Ya-Juan, LU Min, LI Xia, ZHANG Hao-Hao, SUN Yu

2012, 33(06):  1259-1263.  doi:10.3969/j.issn.0251-0790.2012.06.023

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The structures and properties of Ge@C₈₂ were investigated via the density functional theory(DFT) method. The results show that the carbon cage is enlarged and germanium atom shift slightly from the cage center due to encapsulation. The triplet C₂Ge@C₈₂ has the lowest energy. The natural population analysis shows that the electron transfer between C₂C₈₂ and Ge is not evident, and its structure can be represented as C₂Ge@C₈₂. The IR spectrum analysis of C₂C₈₂ and C₂Ge@C₈₂ indicates that the absorption peak of C₂Ge@C₈₂ becomes acute in the range of 1100-1200 cm^-1.



Preparation of Ag/ZnO-SnO₂ by CTAB-assisted and Photocatalytic Degradation of Rhodamine B

LI Li, ZHUO Na, GAO Yu, ZHAO Yue-Hong, LI En-Shuai, ZHAO Li-Jie

2012, 33(06):  1264-1270.  doi:10.3969/j.issn.0251-0790.2012.06.024

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The nano-composite Ag/ZnO-SnO₂ under cetyltrimethylammonium bromide(CTAB) was prepared with a molar ratio of Ag, Zn and Sn of 0.1: 2: 1 by the sol-gel method combined with temperature-programmed treatment. The phase composition, structures and morphologies of the nanocomposite Ag/ZnO-SnO₂(CTAB) were characterized by X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), transmission electron microscopy(TEM), N₂ adsorption-desorption tests and scanning electron microscopy assisted X-ray energy dispersive spectroscopy(SEM-EDS). The results show that the nanocomposite Ag/ZnO-SnO₂ is well wurtzite and rutile structures, and Ag in the nano-composite Ag/ZnO-SnO₂ is metallic Ag⁰. Compared with no CTAB-assisted nanocomposite, the nanocomposite Ag/ZnO-SnO₂(CTAB) has uniformly distribution and shows regularly nano-rods. By the photocatalytic degradation of RhB, under UV and visble light irradiation, the photocatalytic activity of Ag/ZnO-SnO₂ under CTAB-assisted is enhanced, of which is higher than that of Ag/ZnO-SnO₂, ZnO-SnO₂, ZnO and Degussa P-25.



Sum Frequency Generation Vibrational Spectroscopy Study of Serial Short Chain Fatty Acids Liquid/Air Interfaces

HUANG Zhi, GUO Yuan

2012, 33(06):  1271-1277.  doi:10.3969/j.issn.0251-0790.2012.06.025

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The air/pure liquid interfaces of five kinds of short chain fatty acids of acetic acid, propionic acid, butyric acid, pentanoic acid and hexanoic acid were addressed by sum frequency generation vibrational spectroscopy(SFG-VS) under three polarization combinations(ssp, ppp, sps). The vibrational modes of spectra peaks were assigned according to the polarization selection rules. Furthermore, the orientation of the fatty acid molecules at air/liquid interface was calculated. It was found that the orientation angles increase slightly with the increase of the length of carbon chain and the possible mechanism was proposed.



Theoretical Studies on the Effect of Electric Field on the Structures of Metal String Complex Ni₃(dpa)₄Cl₂

TAN Ying, HUANG Xiao, XU Xuan, XU Zhi-Guang

2012, 33(06):  1278-1284.  doi:10.3969/j.issn.0251-0790.2012.06.026

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As a potential molecular wire species, Ni₃(dpa)₄Cl₂ complex with metal string structure was investigated theoretically by density functional theory UBP86 methods incorporating the external electric field along the Ni⁶⁺₃ chain. The results show that there is delocalization throughout the Ni⁶⁺₃ chain and axial ligands Cl. Under the effect of electric field, the distance of bond Ni2-Cl4 increases, distance of bond Ni1-Ni2 decreases, distance of bond Ni1-Ni3 increases and distance of bond Ni3-Cl5 decreases along the direction of electric field. With an increase of the electric field, the molecular energy and the HOMO-LUMO energy gap decrease but the dipole moment increases linearly. When the electric field enhances, the spatial distribution of frontier occupied orbitals moves to the negative potential side with the orbital energy increasing, while that of unoccupied orbitals changes oppositely. Particularly, the frontier orbital delocalized along the Ni⁶⁺₃ chain is more sensitive to the electric field. Moreover, the application of electric field changes the charge distribution. The negative charge moves from Cl5 with low potential end towards Cl4 with high potential end. However, the charges of metals and dpa^- ligands are almost unchanged. The variations of structure and electric charge seem to present a disciplinarian similar to directional movement of electrons in the electrical conduction process.



Density Functional Theoretical Study on Electronic Properties of Lindquist-type Anions [M_6-nMo_nO₁₉]^p-(M=W, Nb, Ta)

SANG Yuan-Mei, YAN Li-Kai, WEN Shi-Zheng, CONG Sha, SU Zhong-Min

2012, 33(06):  1285-1289.  doi:10.3969/j.issn.0251-0790.2012.06.027

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The activated effect of Mo atom on the bond of M-O_t(M=W, Nb, Ta) of substituted systems [W_6-nMo_nO₁₉]^2-, [Nb_6-nMo_nO₁₉]^p- and [Ta_6-nMo_nO₁₉]^p- was investigated by density functional theory(DFT) method. The results show that the bonding energy of M-O_t in [M_6-nMo_nO₁₉]^2-(M=W, Nb, Ta) decrease with the increasing number of Mo atom. Therefore, the M-O_t bond was activated when Mo atom was introduced. While the Mo-O_t bonding energy is less than that of W-O_t, the Mo-O_t bond is easily broken than the W-O_t bond, which was in well agreement with experimental results. For systems [Nb_6-nMo_nO₁₉]^p- and [Ta_6-nMo_nO₁₉]^p-, the bonding energy of Mo-O_t is larger than that of M-O_t bond(M=Nb, Ta). The natural charges on terminal oxygen of Nb-O_t and Ta-O_t are larger than that of terminal oxygen of Mo-O_t. It predicts that Nb-O_t and Ta-O_t prefer to be broken, and easily form Nb≡ ≡N bond and Ta≡ ≡N bond when [Nb_6-nMo_nO₁₉]^p- and [Ta_6-nMo_nO₁₉]^p- react with organic amines.



Preparation of Graphene and Electrocatalysis Oxidation of p-Hydroquinone at Graphene Modified Electrode

HE Chun-Lan, LIU Cheng-Lun, XIE Tai-Ping, WANG Yuan, ZHANG Jing, ZHANG Liang

2012, 33(06):  1290-1294.  doi:10.3969/j.issn.0251-0790.2012.06.028

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The graphene(GN) was prepared by reducing graphene oxide(GO) using ammonia solution, and the electrocatalysis on p-hydroquinone(HQ) was also investigated at graphene-modified electrode(GN/GCE). The molecular structure, interface morphology and electrochemical properties of GN were determined by FTIR, Raman, XRD, SEM, AFM, surface area analysis(BET) and electrochemical methods. The results show that the charge transfer resistance of [Fe(CN)₆]^3-/4- at GN/GCE is 75.0 Ω·cm² decreased by 9 times as compared to that of the bare glass carbon electrode(GCE), indicating that GN has good conductivity. Meanwhile, the oxidation peak potential of HQ has been shifted negatively and its reduction peak potential has been shifted positively, and the peak separation potential(ΔE_p) is decreased by 165 mV with the redox peak currents increasing significantly. It is concluded that the reversibility of HQ improves greatly and GN/GCE holds remar-kable electrocatalytic activity toward HQ. The test method has provided an important inspection for in situ monitoring hazardous matter in food, environment and life fields.



Preparation and Characterization of Composite Polymer Electrolytes Containing Surface-modified Nano Silica

GU Ning-Yu, AO He, PEI Jian-Jun

2012, 33(06):  1295-1300.  doi:10.3969/j.issn.0251-0790.2012.06.029

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Nano silica with carbonate groups were synthesized by the esterification reaction and the structure of the modified nano silica were characterized by FTIR and TGA methods. The composite polymer electrolytes(CPEs) were prepared by introducing the modified nano silica. The thermal and electrochemical performances of the CPEs were studied by DSC and AC impedance. The results show that the addition of modified nano silica enhance the thermal properties and ionic conductivities of CPEs, and meanwhile the lithium ion transference number of CPEs increase up to 0.49. AC impedance results reveal that modified nano silica can also improve the interfacial stability between CPEs and lithium metal electrode.



Zero-shear Viscosity and Critical Concentrations of Aqueous Solution of Partially Hydrolyzed Polyacrylamide

CHEN Kun, LI Hai-Ping, HOU Wan-Guo

2012, 33(06):  1301-1305.  doi:10.3969/j.issn.0251-0790.2012.06.030

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Creep and oscillation experiments were performed to measure the zero-shear viscosity(η₀) and storage modulus(G') of aqueous solution of partially hydrolyzed polyacrylamide(PHPA), respectively. The overlapping concentration(C^*) and crossover concentration(C^*) of PHPA solution were determined through the dependence of η₀ on solution concentration(C). Effects of temperature, pH value and electrolytes(NaCl and CaCl₂) on C^* and C^* were investigated. The results show that as temperature and electrolyte concentration are raised, η₀ and G' decrease while C^* and C^* increase gradually. The higher the electrolyte cation valence is, the more obvious the induced variation of viscosity and critical concentrations of PHPA solution is. With pH value increasing, η₀ and G' increase initially and decrease subsequently while C^* and C^* decrease first and increase afterwards.



Surface-enhanced Raman Scattering of Rhodamine 6G and Crystal Violet Co-adsorbed on Ag/Si-NPA

WANG Yong-Qiang, WANG Hai-Yan, MA Sheng, LI Xin-Jian

2012, 33(06):  1306-1311.  doi:10.3969/j.issn.0251-0790.2012.06.031

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Based on silicon nanoporous pillar array(Si-NPA), an active substrate(Ag/Si-NPA) with strong surface-enhanced Raman scattering(SERS) effect was prepared by an immersion plating method. The surface morphology and structure of Ag/Si-NPA were characterized by field-emission scanning electron microscopy(FESEM) and transmission electron microscopy(TEM). Choosing two important biological dyes, Rhodamine 6G(R6G) and crystal violet(CV), as the target materials and adopting three different adsorbing procedures, the SERS spectra for R6G and CV co-adsorbed on Ag/Si-NPA were detected. It was found that the Raman peaks for CV were completely glossed over by that of R6G when the concentration of both solutions was 10^-7 mol/L, no matter what adsorbing procedure was adopted. The phenomenon was explained based on the experimental conditions and results. When the solution concentrations for R6G and CV were chosen as 10^-9 and 10^-7 mol/L, two groups of characteristic SERS peaks with good separation, well-matched relative intensity and high resolution, corresponding to R6G and CV, respectively, were obtained. Such a SERS spectrum was very helpful for predigesting the indexing and estimating procedure about the characteristic peaks. Our results might provid an investigable route for realizing the SERS detection of multi-dye labeled complex bio-molecule systems.



Preparation and Electrochemical Properties of Polyaniline Nanofiber Modified Graphite Foil

SANG Xiao-Guang, ZENG Fan-Wu, LIU Xiao-Xia

2012, 33(06):  1312-1318.  doi:10.3969/j.issn.0251-0790.2012.06.032

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Polyaniline nanofiber(Nano-PANI) modified graphite foil(GF)(Nano-PANI/GF) was prepared by electrochemical polymerization of aniline on GF electrode. The polymer on the modified electrode Nano-PANI/GF was characterized by FTIR. The morphologies of the modified electrode were investigated by SEM. The Nano-PANI/GF electrode made through cyclic voltammetric scans in a solution of 0.1 mol/L aniline and 1.0 mol/L HCl showed good electroactivites in 0.1 mol/L phosphate buffer solution(pH=6.9). The electrocatalytic properties of the modified electrode toward ascorbic acid oxidation were studied through cyclic voltammetry and potentiometry. The current for ascorbic acid oxidation on the modified electrode at 0.2 V showed linear response to the concentration of ascorbic acid in the range of 1.7-2.0×10³ μmol/L. The detection limit of ascorbic acid on the modified electrode is 1.7 μmol/L(S/N=3).



Molecular Dynamics Simulation on Adsorbing Behavior of Anionic Gemini Surfactants at Decane/Water Interface

LIU Mei-Tang, PU Min-Feng, MA Hong-Wen

2012, 33(06):  1319-1325.  doi:10.3969/j.issn.0251-0790.2012.06.033

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Molecular dynamics simulations were performed to investigate the adsorbing behavior of anionic sulfonate Gemini surfactants at oil/water interface. Effects of spacer on the aggregation and interfacial properties of surfactants were studied in detail. The interfacial structure and density profiles of adsorbents show the exis-tence of Gemini surfactants monolayer. The interfacial thickness increased significantly and the interface formation energy decreased when incorporating the Gemini surfactants into the oil/water interface. Better interfacial properties are also found in this work when the spacer has six carbons. Except for water molecular diffusion properties, only little effect of spacer on the adsorbing structure and properties of water and Na⁺ surroun-ding the interface of Gemini surfactants are found.



Comparison of ZrO₂/MCM-41 and ZrO₂/AC Catalysts in Hydrogen Transfer Reaction of Acetophenone

YUAN Jian, ZHANG Bo, TANG Ming-Hui, LU Han-Feng, CHEN Yin-Fei

2012, 33(06):  1326-1332.  doi:10.3969/j.issn.0251-0790.2012.06.034

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Zirconia(ZrO₂) was supported on active carbon(AC) or siliceous MCM-41 mesoporous materials(ZrO₂/MCM-41) respectively through the impregnation method, At the same time, these samples were cha-racterized by XRD, N₂ adsorption-desorption, XPS, TG-DSC and FTIR spectra of adsorbed pyridine methods. Their catalytic activities in the Meerwein-Ponndorf-Verley(MPV) reduction of acetophenone with α-propanol as a hydrogen donor were investigated, and compared to that of hydrous zirconia to study the support effect on their catalytic activities. The results showed that catalytic activity was significantly improved upon loading zirconia on MCM-41 support, due to the formation of Si-O-Zr bond between zirconia and MCM-41 supported, which resulted in the formation of highly dispersed amorphous zirconia in the catalyst, consequently a marked increase of the amount of the Zr-OH group, the strengthening of Lewis acidity and an appearance of Brnsted acid sites. In contrast to ZrO₂/MCM-41, no obvious increase of catalytic activity was observed after loading zirconia on AC support owing to the weak interaction between zirconia and AC support, which resulted in the lower dispersion of zirconia on AC support, consequently a less increase of number of Zr-OH groups and weak Lewis acidity. However, ZrO₂/AC calcined at higher temperature(400-600 ℃) still retained steady activity, which may be due to the dredging of pores in AC during the calcination, and the increase of concentration of acetophenone near the active sites via the π-π electron interaction between the benzene ring in the acetophenone and graphite layer of AC support.



Polymer Chemistry

Synthesis of Imidazolium Ionic Liquid/Styrene Random Copolymer and Its Nanocomposite with CdTe Quantum Dot

LI Xue, NI Xu-Feng, LIANG Zhen-Hua, SHEN Zhi-Quan

2012, 33(06):  1333-1338.  doi:10.3969/j.issn.0251-0790.2012.06.035

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Side-chain imidazolium-functionalized random copolymer P(MMEIM⁺Cl^--co-St) was synthesized by free-radical copolymerization of 1-methyl-3-(2-methacryloyloxy ethyl) imidazolium chloride(MMEIM⁺Cl^-) and styrene(St) with azodiisobutyrounitrile(AIBN) as initiator. The structure of random copolymer was characterized by FTIR, ¹H NMR and GPC analyses. By the electrostatic interaction between positively charged imidazolium-functionalized P(MMEIM⁺Cl^--co-St) and the negatively charged aqueous CdTe quantum dots(QDs), fluorescent nanocrystal-polymer composites CdTe/P(MMEIM⁺Cl^--co-St) were prepared conveniently. UV-Vis absorption and photoluminescence(PL) spectra indicated the photochemical stability and strong fluorescent emission of CdTe/P(MMEIM⁺Cl^--co-St) composites. The transmission electron microscopy(TEM) photograph shows that the CdTe QDs in composites are monodisperse, uniform and no significant surface deterioration or aggregation of the QDs occurred during the composite synthesis.



Synthesis and Fluorescence Properties of Polymerizable 1,8-Naphthalimide Derivatives Doped Polysiloxane Materials

SONG Jian-Hui, WU Meng, YU Yi-Hua, CHEN Qun, XU Min

2012, 33(06):  1339-1343.  doi:10.3969/j.issn.0251-0790.2012.06.036

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Three polymerizable 1,8-naphthalimide derivatives were synthesized and their photophysical properties in DMSO solution were determined. ¹H NMR spectra of these compounds revealed the electronic environment surrounding the hydrogen nucleus which is proved to be related to their photophysical properties. Highly fluorescent polysiloxane materials were prepared by condensation of polymerizable 1,8-naphthalimides derivatives with γ-aminopropyl triethoxysilane(APTES) by the sol-gel process. It was found that all of the 1,8-naphthalimides derivatives with different substituent at C-4 position possess the best fluorescence intensity while doped in polysiloxane at molar fraction of 0.06%. ²⁹Si MAS NMR and fluorescence measurement results show that the degree of condensation of polysiloxane also affect the fluorescence of materials, which hints that the molecular motion is the stronger factor than substituent effect on the fluorescence of the solid materials.



Synthesis, Structure and Performance of Soluble Polyaniline by CPO-catalyzed Oxidation Using Small Molecule as Dopant or Polyelectrolyte as Template

WANG Ya-Li, NIE Yan-Yan, JIANG Yu-Cheng, HU Man-Cheng, LI Shu-Ni, ZHAI Quan-Guo

2012, 33(06):  1344-1349.  doi:10.3969/j.issn.0251-0790.2012.06.037

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A green enzymatic approach for the synthesis of soluble polyaniline(PANI) from p-phenylene diamine(PPD) monomer by chloroperoxidase(CPO)-catalyzed H₂O₂-oxidation was proposed. The perfor-mance of aim product was improved compared to that of eigenstate polymer by the introduction of small molecule as dopant or polyelectrolyte as template, which was testified by UV-Vis spectra, cyclic voltammetry curve, electron microscope scanning, thermal gravimetric analysis and conductivity measurement. Sodium perchlorate was screened as the most effective dopant, and the corresponding product when n(PPD): n(NaClO\-4)=1: 1 had fine layer structure and strong reversible redox capacity; The PANI obtained with polystyrene sulfonate(SPS) as the template had the best thermal stability and solubility as well as maximum conductivity. The enzymatic polymerization was analyzed according to the structure of active site in CPO.



Surface Modification of Hydrophobic Acrylic Intraocular Lens by Ammonia Low-temperature Plasma

ZHENG Zhi-Wen, DENG Kai-Min, REN Li, WANG Ying-Jun

2012, 33(06):  1350-1354.  doi:10.3969/j.issn.0251-0790.2012.06.038

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Hydrophobic acrylic intraocular lens is a novel soft material, which is different from the traditional polymethyl methacrylate(PMMA) lens. Surface modification of the lens surface with ammonia low-temperature plasma treatment was performed and characterized in order to enhance the hydrophilicity and biocompatibility. The results show that NH₃ plasma treatment produce the most hydrophilic surface among O₂, Ar and NH₃ gases. The optimal modification time and power were 120 s and 150 W, respectively. XPS analyses further verified that the polar groups were immobilized on the lens surfaces. The AFM images of the treated samples show rougher surfaces with a significant increase in root mean square roughness(RMS). Transmittance exhibited small changes after modification in general. However, a larger power led to a sharp drop in the transmittance. According to the aging effect test, hydrophobic recovery occurred following the modification and tended to be stable after 14 d.



Superhydrophobic Conducting Polyaniline Prepared via Interfacial Polymerization

WANG Liang, DING Chun-Mei, ZHU Ying, WAN Mei-Xiang, JIANG Lei

2012, 33(06):  1355-1359.  doi:10.3969/j.issn.0251-0790.2012.06.039

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Three-dimensional(3D) micro/nanostructures of polyaniline(PANI) were self-assembled by template-free method combined with interfacial polymerization in the presence of perfluorosebacic acid(PFSEA) as dopant. The 3D micro/nanostructures of PANI show both electrical conductivity and superhydrophobicity. It was proposed that the aniline filled bi-layer micelles composed of PFSEA/An salt were served as the soft-templates of the self-assembled nanofibers, then those nanofibers were self-assembled to form 3D-microstructures by the intermolecular interactions including hydrogen bonding and hydrophobic interaction as the driving forces. Moreover, their morphology and size can be controlled by changing the concentration and the molar ratio of aniline and oxidant. The method is a facile approach to prepare conducting polymer 3D architectures assembled by 1D-nanostructure.



Preparation of Cholesterol-graft-poly(D,L-lactic acid)/ Poly(D,L-lactic acid) Composite Nanofiber Membranes by Electrospinning

LUO Bing-Hong, LI Jian-Hua, YANG Jing, XU Chong-En, TIAN Jin-Huan, ZHOU Chang-Ren

2012, 33(06):  1360-1366.  doi:10.3969/j.issn.0251-0790.2012.06.040

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Cholesterol-graft-poly(D,L-lactic acid)(CHOL-g-PDLLA ) oligomer was synthesized by the ring-opening polymerization of D,L-lactide using stannous 2-ethylhexanoate as catalyst and cholesterol(CHOL) as co-initiator, and the liquid crystalline properties was observed by polarizing microscope and differential scanning calorimetry. Then, CHOL/PDLLA and CHOL-g-PDLLA/PDLLA composite nanofiber membranes were prepared by electrospinning. The micrograph, interfacial compatibility, porosity, tensile properties and cellular compatibility of the composite nanofiber membranes were studied. The results show that CHOL-g-PDLLA is a thermotropic cholesteric liquid crystal with liquid crystal temperature range of 21.8-74.5 ℃. CHOL-g-PDLLA/PDLLA composite nanofiber membranes with good fiber micrograph, smooth surface and porosity of 70% to 75% were obtained, and the interfacial compatibility was significantly better than that of CHOL/PDLLA. With the content of CHOL or CHOL-g-PDLLA increased, the tensile strength of CHOL/PDLLA and CHOL-g-PDLLA/PDLLA composite nanofiber membranes both decreased, but the tensile strength of the latter is always greater than that of the former. The results of mesenchymal stem cells culture in vitro indicate that the cellular compatibility of the CHOL-g-PDLLA/PDLLA composite nanofiber membranes is very good, and better than those of pure PDLLA and CHOL/PDLLA nanofiber membranes.