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    10 March 2006, Volume 27 Issue 3
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    高等学校化学学报2006年第27卷第3期目次
    2006, 27(3):  0.  doi:
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    Articles
    Optical Properties of Mesoporous MCM-41 Powders and Fibers Doped with Laser Dye Coumarin 151
    CHEN Yue, LI Xiao-Tian, GU Li-Mi-Na, LI Nan, ZHU Guang-Shan, QIU Shi-Lun
    2006, 27(3):  397-400. 
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    In this paper,laser dye molecules,such as Coumarin 151 molecules,were doped into mesoporous MCM-41 powders and fibers using crystallization inclusion method. The composites were characterized by Leica microscope,SAXRD,UV-Vis diffuse reflection spectrum. The fibers which doped with Coumarin 151 were 20 μm in width and 3\_5 mm in length. Both the powder and the fibers doped with Coumarine 151 were blue-shift in UV-Vis spectrum compared with the dyes in solid. Both the composites have luminescent properties.

    Synthesis and Spectral Properties of Eu2+/Ce3+ Doped Potassium Magnesium Fluoride Nanoparticles
    ZHU Guo-Xian, YAN Jing-Hui, MO Feng-Shan, LIAN Hong-Zhou, SHI Chun-Shan
    2006, 27(3):  401-405. 
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    Phosphors of KMgF3∶Eu2+, KMgF3∶Ce3+and KMgF3∶Eu2+,Ce3+nanoparticles were synthesized in cetyltrimethylammonium bromide(CTAB)/2-octanol/water microemulsion systems. X-ray diffraction(XRD) patterns was used to identify the formation of KMgF3 phase without detectable impurity. Environment scanning electron microscopy(ESEM) images show the even size distribution of the nanoparticles with pellet morphology. Photoluminescence characteristics of the rare earth ions doped nanoparticles were investigated and compared with that of the polycrystalline products prepared by solid state reaction at a high temperature. The emission band of the Ce3+ could only be observed due to absorbing the exciting energy competitively between the Eu2+ and Ce3+ in co-doped system of KMgF3 nanoparticles,while the emission peak of the Eu2+could only be observed due to energy transfer from Ce3+ to Eu2+appearing in the KMgF3∶Eu2+,Ce3+polycrystalline powder. The mechanism on energr transfer from Ce3+ to Eu2+ in polycrystal and from Eu2+ to Ce3+in nanocrystal KMgF3∶Eu2+,Ce3+was discussed by means of Eu2+ excitation spectrum and Ce3+emission spectrum.

    Studies on the Self-arrangement of β-FeOOH Nanowires and the Formation Mechanism
    WANG Xiao-Juan, ZHANG Xin-Tang, JIANG Xiao-Hong, LIU Bing, WANG Hong-Zhe, LI TYun-Cai, HUANG Ya-Bin, DU Zu-Liang
    2006, 27(3):  406-409 . 
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    β-FeOOH nanowires were synthesized via hydrolysis of iron(Ⅲ) salts at room temperature. The morphology and structure of as-prepared sample were investigated by Transmission Electron Microscopy(TEM) and X-ray Diffraction(XRD). The characterization results showed that the nanowires were well-crystallized tetragonal β-FeOOH nanowires growing along ［001］ axis with diameters about 60 nm and lengths up to 4_5 μm respectively. The formation mechanism of the nanowires was also proposed based on the results of experiment. Moreover,the nanowires can arrange perpendicularly or abreast together to form special patterns through self\|assembly,which the magnetic interaction between them should be the main causation.

    Synthesis and Characterization of L-Glutamic Acid Bridged Porphyrin and Its CD Spectrum
    GUO Xi-Ming, SU Lian-Jiang, YU Lian-Xiang, SHI Tong-Shun
    2006, 27(3):  410-413. 
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    The L-glutamicacyl dichloride was prepared by the reaction of L-glutamic acid(NH2 was protected by using acetyl group) with SOCl2,then reacted with 5-(4-hydroxyphenyl)-10,15,20-triphenylporphyrin,to give L-glutamic acid bridged diporphyrins. The compound was confirmed by using IR,1H NMR,UV-Vis and elemental analysis. The chiral characteristics of the dimmer was studied by the circular dichroism(CD) spectrum.

    Effects of Co-solvent on the Uniformity of Pore Size of ZnO Bulk Porous Nanosolids
    LI Mei, SUN Hai-Yan, LIU Xiu-Lin, XU Gong-Yan, WANG Cheng-Jian, CUI De-Liang, JIANG Min-Hua
    2006, 27(3):  414-418. 
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    Using sodium dodecylsulfate solution(SDS) as the pore-forming agent and ZnO nanoparticles as the starting material,ZnO porous bulk solid was successfully prepared by a novel solvothermal hot press method. Furthermore,the effects of the addition of polyethylene glycol 400(PEG-400) into the solvent were also investigated. It was found that,the pore diameter of the ZnO porous bulk solids largely decreased when PEG-400 was added into the solvent. Besides,the specific surface area and porosity also decrease correspondingly. On the other hand,the uniformity of the channel diameter of ZnO bulk porous nanosolids was greatly improved.

    Synthesis of New Mixed-ligands Amphiphilic Ruthenium Complex and Its Naked-eye Detectable Recognition of Hg2+
    LI Xiang-Hong, DUAN Xin-Fang, LI Fu-You, HUANG Chun-Hui
    2006, 27(3):  419-423. 
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    4,4′-Di(p-methylphenyl)-2,2′-bipyridine was synthesized via modified routine with a high yield of 15.3%,and was used as a ligand to form a new mixed-ligand amphiphilic ruthenium complex,cis-N,N-4,4′-di(p-methylphenyl)-2,2′-bipyridine-N,N-4,4′-dicarboxy-2,2′-bipyridine-N,N-dithiocyanato ruthenium(Ⅱ). This new mixed-ligands amphiphilic ruthenium complex was characterized by IR,UV-Vis,1H NMR and Maldi-TOF MS spectra and firstly used to detect Hg2+Its MLCT absorption(530 nm) was blue-shifted to 485 nm when Hg2+ was added to DMF-ethanol(volume ratio 1∶9) solution of the complex. The complex was combined quantitatively with Hg2+ not with other metal cations by the molar ratio of 1∶1,indicating that it can be used as a selective naked-eye sensor for Hg2+Its detective limit is 0.5×10-6 mol/L.

    Fluorescent Characterization of Peroxynitrite-induced Thiyl  Radicals
    DANG Ya-Min, GUO Xiang-Qun
    2006, 27(3):  424-427. 
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    A spin-labeling fluorophore(Ac-Tempo·),formed by combining with an acridine with a paramagnetic nitroxide(4-hydroxyl-2,2,6,6-tetramethylpiperidinyl-1-oxy),was explored for peptide-based thiyl radicals generated through the reaction between gluththione and peroxynitrite. Ac-Tempo·,a weak fluorescent compound,showed a dramatic increase in fluorescence intensity after interaction with thiyl radicals,and could be employed to probe peptide-based thiyl radicals.

     Fabrication of Micro Flow Through PCR Chip by Excimer Laser and Its Application
    YAO Li-Ying, QI Heng, CHEN Tao, WEN Si-Yuan, Bo Xiao-Chen, CHEN Su-Hong, WANG Sheng-Qi, ZUO Tie-Chuan
    2006, 27(3):  428-431. 
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    A cheap PMMA was chosen as the substrate instead of expensive silicon or glass,and a 248 nm excimer laser with flexible and auto character replaced complex lithography as a new fabrication technique.  A PMMA(48 mm×67 mm×1 mm) based micro flow through PCR chip with 20 cycles was fabricated at 19 kV and 18 mm/min excimer laser parameters.  The section of the microchannel was trapezoid,and its bottom surface roughness was less than 0.5 μm.  The microchannel had a width of 104 μm,a depth of 56 μm,and a length of 2 060 mm. It cost about 110 min to finish the total length.  Then the chip was bonded together with another cover chip at 105 ℃,160 N and 20 min parameters.  It could endure 0.85 MPa pressure and seal micro fluid well after sample injection experiment.  In the end,the chip was integrated via the temperature control system.  Three micro PID temperature controllers were chosen to control the temperature and gained ±0.2 ℃ temperature control precision.  The temperature grads between the three temperature zones were 16.5  and 22.2 ℃,respectively.  Finally 170 bp DNA fragments was amplified by using this chip.

    Studies on the  Interaction of Trypsin with Some DNA and Their Analytical Application by Resonance Rayleigh Scattering Spectra
    LI Shan, LIU Zhong-Fang, LIU Shao-Pu
    2006, 27(3):  432-437. 
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    When the trypsin interacts with herring sperm DNA(hsDNA),salmen sperm DNA(sDNA) and calf thymus DNA(ctDNA) to form the binding products,the Resonance Rayleigh scattering(RRS) are obvious enhanced remarkably and new RRS spectra appear. They have similar characteristics of RRS spectra,the maximum RRS peaks are at 307 nm(hsDNA,sDNA) and 290 nm(ctDNA),and the other peaks are  at 350 nm. As the scattering intensity is proportion to the concentration of DNA or trypsin respectively,the reaction can also be used as a new method for the determination of trypsin with DNA and for the determination of DNA with trypsin. When it  is used  for the determination of  DNA with trypsin,the linear range are 1.4×10-3—2.3 μg/mL(hsDNA),2.1×10-3—2.5  μg/mL(sDNA) and 3.5×10-3—1.9 μg/mL(ctDNA),and the detection limits are 0.4 μg/mL(hsDNA),0.7  μg/mL(sDNA) and 1.1 μg/mL(ctDNA),respectively. When it is used for the  determination of trypsin with hsDNA,the linear range is between 0.1 ng/mL and 30.0 μg/mL,and its detection limit is 39.0 ng/mL. In this  paper,the optimal interaction conditions,the affecting factors,the properties of analytical chemistry of the binding complex and the binding ratio of trypsin with DNA were investigated. The binding mode,binding ratio of trypsin with DNA and the reasons for the enhancement of RRS intensity are also discussed. A highly sensitive,simple and quick method for the determination of trace amount of DNA with trypsin as a RRS probe was developed.

    Investigation on the Acute Biochemical Effects of Light Rare Earths(Lanthanum and Cerium) by NMR-Based Metabonomic Approaches
    LI Zhong-Feng, WU Hui-Feng, ZHANG Xiao-Yu, LI Xiao-Jing, LIAO Pei-Qiu, LI Wei-Sheng, PEI Feng-Kui
    2006, 27(3):  438-442. 
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    1H NMR spectroscopy and pattern recognition method were used to assess acute biochemical effects of light rare earths. Male Wistar rats were treated with both La(NO3)3 and Ce(NO3)3 at doses of 2,10 and 50 mg/kg body weight. Serum samples from the rats dosed with the two kinds of light rare earths were gained after 48 h and analyzed by 600 MHz 1H NMR spectra. Each NMR spectra was data-processed to provide 238 intensity-related descriptors as input coordinates in a multidimensional space and analyzed by pattern recognition method. Many low-molecular weight metabolites were identified by 1HNMR spectra of rat serum. An increase in ketone bodies,creatinine,lactate,succinate and various amino acids(valine,leucine and glutamine) were found from the higher doses(10 and 50 mg/kg body weigh) of rare earths-treated groups,together with a decrease of glucose in the serum from Ce(NO3)3-dosed groups. Those results may mean that high-dosage of La and Ce impair the specific region of liver. The similar toxicities with various mechanisms for La and Ce were implicated by NMR-based metabonomic approach. Ce(NO3)3 exhibited a higher toxicity than La(NO3)3 at the same doses.

    Chemical Component Study of Herb Pairs in Traditional Chinese Medicine
    --Analysis of Volatile Oil in Rhizoma Ligustici Chuanxiong-Radix Paeoniae Rubra by GC-MS and Chemometric Resolution Method
    LI Xiao-Ru, LIANG Yi-Ceng, YANG Hui, GUO Fang-Qiu, LI Xiao-Ning, ZENG Zhong-Da
    2006, 27(3):  443-448 . 
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    The volatile chemical components of herb pair Rhizoma Ligustici Chuanxiong-Radix Paeoniae Rubra(RLC-RPR) were analyzed by gas chromatography- mass spectrometry(GC-MS),chemometric resolution method(CRM),and overall volume integration methods. By using these methods upon two-dimensional data,52,33,and 61 volatile chemical components in the essential oil of RLC,RPR,and herb pair RLC-RPR were,respectively,determined qualitatively and quantitatively,accounting for 95.14%,95.82% and 90.18% of the total contents of the essential oil of RLC,RPR and herb pair RLC-RPR,respectively. The experimental results show that the volatile chemical components of herb pair RLC-RPR in number are almost the addition of that of two single drugs RLC and RPR,but are changed in contents.

    Comparison of Speciation Patterns of Heavy Metals in Yitong River Sediments under Anoxic and Oxidized Conditions
    LU Yong-Zheng, DONG De-Meng, FU Yao, SHEN Xiu-E, YUAN Mao, SUN Wen-Tian
    2006, 27(3):  449-453. 
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    Anoxic sediments could be oxidized by extraction reagent and by air in dryness pre-treatment procedure,which resulted in different impact on speciation patterns of heavy metals during the sequential extraction procedure. The speciation patterns of Cu,Pb,Zn,Ni in different depths sediments in  Yitong River under Ziyou Bridge of Changchun City were investigated by the improved Tessier sequential extraction schemes under anoxic and oxidized conditions,and AVS(acid volatile sulfide)and SEM(simultaneous extract metals)were analyzed too. The experiment results demonstrate that the percentage of Cu associated with organic/sulfide phase reduced 40% and that of Mn-oxide phase increased remarkably after dryness and grind pre-treatment procedure of sediments; the percentage of Pb,Zn,Ni in organic/sulfide phase slightly descended but less than Cu,and the redistributions are different for three metals. Comparing amounts of metals in SEM with that in organic/sulfide phase,the data indicate that Cu is mainly associated with organic materials other than sulfides,but Pb,Zn,Ni,Fe,Mn are predominantly associated with sulfides in anoxic sediments,and the speciation patterns for the metals were influenced on different degrees by extraction reagents.

    Synthesis and Biological Activity of 5,7-Dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-oxoacetohydrazone Derivatives
    CHEN Qiong, LONG De-Qing, CHENG Jing, LI Jing, LIU Zu-Meng, YANG Guang-Fu
    2006, 27(3):  454-459. 
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    Fifteen novel 5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-oxoacetohydrazone derivatives and ten novel (R)-5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-2-oxo(α-methyl)acetohydrazone derivatives were designed and synthesized by using 5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidin-|2-methylthioether as the starting material. All synthesized compounds were confirmed by elemental analysis,  MS and 1H NMR. The preliminary bioassay indicates that some of them display good herbicidal and fungicidal activities. Those compounds with chiral center display better bioactivities.

    Synthesis of Phenylenedimethylene Bis(guanidiniums) Derivatives
    SONG Wei, LU Xiao-Feng, LU Guo-Yuan
    2006, 27(3):  460-463. 
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    Naturally occurring and synthetic compounds containing guanidine display a wide range of biological activities and are used as a receptor for organic anions. This paper reports the synthesis of phenylenedimethy-lene diamines and bis(guanidiniums) derivatives. The phenylenedimethylene diamine derivatives were prepared by the reaction of phenylenedimethylene dichloride with sodium diformamide and then hydrolyzing with hydrochloric acid/ethanol solution. The diamines were respectively treated with S-methylisothiourea sulfate to give the corresponding phenylenedimethylene bis(guanidiniums) sulfate,and then they were converted to the corresponding chlorides by ion-exchange process. 1H NMR spectra and ESIMS data indicate that they display a stronger interaction with organic anions.

    Syntheses and Structures of Some Functionalized Optically Active Butanediol Derivatives
    HE Lan, ZHANG Wei, LIU Yu-Mei, LI Ming, CHEN Qing-Hua
    2006, 27(3):  464-467. 
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    Through the use of the synthetic strategy outlined in this article,the chiral 5-(R)-［(1R,2S,5R)-(-)-menthyloxy］-4-(R)-(heterocyclic base group)-2(5H)-furanones(5) containing one stereogenic center were obtained via the asymmetric Michael addition reaction of heterocyclic bases with the chiron 3. Adducts 5 were reduced to give the functionalized compounds with optical purity,2-(R)-(heterocyclic base group)-1,4-butanediols(6) in good yields with e.e.≥98%. The chemical structure of compound 6 was readily confirmed by elemental analysis data and spectroscopic data. The proposed structures of optically active compounds 6 were consistent with the stereochemistry and the configurations of their molecules were further confirmed by its X-ray crystallography. These results provided a new synthetic strategy to the functionalized optically active butanediol derivatives. This aim of the present study would be to propose further groundwork for any future applications of the functionalized optically active butanediols to the synthesis of important chiral acyclic nucleoside analogues and organic ligands as well as chiral blockings for synthesizing some supramolecular system and chiral medicines.

    Synthesis and Bioactivity of Salicylic Acid 3-N′-Benzyloxy-carbonyl-β-aminobutyric Ester
    ZANG Hong-Jun, LI Zheng-Ming, NI Chang-Chun, SHEN Zhou, FAN Zhi-Jin, LIU Xiu-Feng
    2006, 27(3):  468-471. 
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    The plant activators such as salicylic acid and D,L-β-aminobutyric acid can induce systemic resiatance acquired in the treated plants against following pathogen attack. Utilizing coordination of active moieties,the chemical activators were designed to incorporate some structural moieties from β-aminobutyric and salicylic acid ester. Nine new compounds were prepared,whose structures were confirmed by elemental analysis and 1H NMR. The biocactivity of them was tested and the results indicate that several compounds show a certain induced activity against pathogen infection.

    Synthesis of Eu(Ⅲ) and Tb(Ⅲ) Complexes with Novel Pyridine-2,6-Dicarboxylic Acid Derivatives and Their Fluorescence Properties
    TANG Rui-Ren, YAN Zi-Er, GUO Can-Cheng, LUO Yi-Ming
    2006, 27(3):  472-477. 
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    Starting from pyridine-2,6-dicarboxylicacid(DPA),a series of novel pyridine-2,6-dicarboxylic acid derivatives were synthesized. In these compounds,4-(hydroxymethyl)pyridine-2,6-dicarboxylate(4-HMDPA) and 4-{［bis(carboxymethyl)amino］ methyl}pyridine-2,6-dicarboxylate(4-BMDPA) were used as multifunctional ligands to coordiate with Tb(Ⅲ) and Eu(Ⅲ) and their complexes were prepared. The fluorescence properties of the solid complexes and their solutions were investigated in detail. The results indicate that the weak election-withdrawing group 4-hydroxymethyl in 4-position of pyridine in 4-HMDPA could weaken the fluorescence intensity of the lanthanide complexes. The contradistinctive experimental results show that the fluorescence intensities of these complexes are related to pH value of the aqueous solution and the dipole moment of solvent molecule: in the neutral aqueous solution,the fluorescence intensities of these complexes were strongest,while the less the dipole moment was,the stronger the fluorescence intensity was. 4-BMDPA is the better sensitizer and may be used as time-resolved fluorommunoassay.

    Preparation of Antitumor Compound 20(S)- Protopanaxidiol by the Method of Alkali Catalyzing Degradation
    LI Xu-Wen, JIN Yong-Ri, GUI Ming-Yu, ZHANG Han-Qi, ZHANG Long-Qing
    2006, 27(3):  478-481. 
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    To prepare 20(S)-protopanaxidiolone natural sapogenin in Panax Ginseng C.A.,the method of alkali catalyzing degradation was used.  20(S)-Protopanaxidiol was separated and it′s structure was characterized.  The total saponins from leaves and stems of Panax qinquefolium L.  and strong alkali were solved in  an organic solvent  with a high boiling point,then the degradation was performed at  high temperature and common pressure.  The optimal condition of degradation was confirmed through orthogonal experiment.  20(S)-Protopanaxidiol was separated and purified by extraction,column chromatography and recrystal from the degradation products.  The obtained yield of 20(S)-protopanaxidiol was 5.01%  accounting for the total saponins and the purity  of 20(S)-protopanaxidiol was 98.56%.  The structure of the compound was elucidated by characteristics and spectral analysis as 20(S)-protopanaxidiol.  The characteristics of the method were proved to be high yield,high purity and low costing in  20(S)-protopanaxidiol preparation. 

    Contents
    A New Method for the Synthesis of α-Acetyl Ketene Dithioacetals
    ZHAO Yu-Long, LIU Qun, ZHANG Wei, YU Hai-Feng, LIU Yu, LIN Chun
    2006, 27(3):  482-484 . 
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    The α-acetyl ketene dithioacetals 2,which bear various alkylthio groups,are a kind of important intermediates in organic synthesis. In this paper,dithioacetals 2 were prepared in very high yields (90%—100%) via the deacetylation reaction of the corresponding α,α-diacetyl ketene dithioacetals 1 in the presence of concentrated sulfuric acid. This reaction involves an in-situ electrophilic addition-deacetylation mechanism and shows the nucleophilicity of the α-carbon atom in α-oxo ketenedithioacetals. Meanwhile,when the reaction time was prolonged to 22—25 h,the β-keto thiolesters 3a and 3c were produced in good yields.

    Preparation and Identification of Series of Oligomannuronates
    LIU Bin, WANG Chang-Yun, ZHANG Hong-Rong, WANG Bin-Gui, WEI Yu-Xi, KANG Kai, LI Liang, YU Guang-Li, GENG Mei-Yu, GUAN Hua-Shi
    2006, 27(3):  485-487. 
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    A series of oligomannuronates with series degree of polymerization(DP=2-8) were prepared by acid hydrolysis from alginate-derived homopolymannuronate blocks,and the structures of the oligosaccharides were analyzed. The macromolecule of alginate was treated by partial acid hydrolysis and fractionated at pH=2.85 resulting in homopolymannuronate blocks. The homopolymer was degraded by acid hydrolysis,and the oligosaccharides were separated and purified by gel chromatography. The oligosaccharides were characterized by fluorophore-assisted carbohydrate electrophoresis(FACE),and the structures of derived oligomannuronates were determined by ESI-MS,NMR as well as FTIR analysis.

    Articles
    Aromaticity of Various Possible Isomers of C36X(X=O,NH,S)
    Ablikim Kerim
    2006, 27(3):  488-493. 
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    The topological resonance energy method was applied to all the open structure isomers(both cations and anions) of C36X(X=O,NH,S) to investigate their aromaticity. The calculation results show that: (1) the aromaticity of C36X are higher than C36. (2) The C36X cations with negative resonance energies are predicted to be antiaromatic,whereas the C36X anions with positive resonance energies possess aromatic character. (3) Among the D6h and D2d isomers of C36,the most stable members are those with heteroatoms X added to the 5-5 bond. The possible way for preparing stable metallofullerenes from the anions of C36X is discussed. The aromaticity of C36X cations and anions are interpreted.

    Theoretical Studies on Proton Transfer Reactions of 6-Methyl-4-hydroxy Pyrimidine Monomer and Dimer
    DIAO Ji-Yang, ZHOU Zi-Yan, SU Zhong-Min, XIE Yu-Zhong, WU Xue
    2006, 27(3):  494-497. 
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    Density Functional Theory(DFT) of quantum chemistry method was used to investigate the proton transfer reactions of 6-methyl-4-hydroxy pyrimidine monomer and dimer. By studying the potential energy surface of the isomerization,it was found that there were 9 monomer isomers and 9 transition states in possible reaction pathways. The most stable structure of monomers was analyzed. The lowest and largest reaction activation energy were 22.06 and 356.55 kJ/mol,respectively. The most possible reaction pathways could proceed at room temperature. Two dimers and their transition states were also investigated and it was found that all dimer were more stable than the corresponding monomers. The reaction activation energy of the dimer tautomerization was less than that of the corresponding monomer. Hydrogen bond played an sticking role in those changes and the energies of hydrogen bond were calculated from the total energies of monomers and dimers.

    Electrochemical Properties of  Films of C60  Derivative Modified with  Crown Ether
    ZHANG Hua, NING Bin, WU Yue-Qin, FAN Lou-Zhen, GUO Zhi-Xin
    2006, 27(3):  498-501 . 
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    The electrochemical properties of dibenzo-18-crown-6-C60(DBCFP) films were studied by simultaneous cyclic voltammetry and electrochemical quartz crystal microbalance(EQCM) in acetonitrile solutions containing different supporting electrolytes. The electrochemical properties and the stability of DBCFP film were much different from that of  C60 film due to the 18-crown-6 group with large size and soft property. For the sake of comparison,the electrochemical properties of another C60 derivative(PSF) with rigid perylene group were also investigated. A mechanism for electrochemical process of DBCFP film in TAB+ solution was proposed.

    Measurement of Diffusion Coefficients of Water,Methanol and Ethanol Solvents at Infinite Dilution in the PVA Membrane Material
    JIANG Zhen, LI Ji-Ding, ZENG Chu-Yi, CHEN Jian, CHEN Tian-Quan, CHEN Cui-Xian
    2006, 27(3):  502-505. 
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    Gas chromatography is a new,fast,accurate and convenient technique for studying the relationship between small molecule solvents and polymer membrane materials. Many parameters of dissolution and diffusing characters of a small molecule in a polymer can be measured by this method. The retention time and the peak widths at half-height of water,methanol and ethanol in the stationary phase of PVA were obtained in this work. The diffusion coefficients of the small molecule solvents at infinite dilution were calculated with van Deemter equation. The graphs plotted according to the results of the diffusion coefficients of the three small molecule solvents at infinite dilution vs. temperatures were in agreement with the Arrhenius equation. The variance in the diffusion coefficients at infinite dilution of three small molecule solvents was analyzed according to the differences in molecular size.

    Metal Ion Sensing Properties of BAEAHQA/MCM-41 Assembly
    ZHANG Hui-Dong, ZHANG Ping, SUN Ying-Hui, YE Kai-Qi, ZHANG Jing-Ying, WANG Yue
    2006, 27(3):  506-509. 
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    The quinacridone derivative 5,12-bis［6-(2-amino-ethylamino)-hexyl］ qunacridone(BAEAHQA) which can be used as chelate ligand to coordinate with metal ions,was successfully incorporated into mesoporous molecular sieve MCM-41. The emission spectra indicate that BAEAHQA/MCM-41 emits a great yellowish-green light,which is similar with BAEAHQA in liquid state. And metal ions could quench the luminescence of BAEAHQA/MCM-41,especially when Co2+ ions exist,the luminescence of BAEAHQA/MCM-41 was quenched completely. It is suggested that BAEAHQA/MCM-41 can be used as the metal ions sensing material.

    Theoretical Studies on Ground State Structure, Electronic Energy Level and Absorption Spectra of PPV Oligomers with Biphenyl Bridge
    XU Hai, YANG Bing, HE Feng, XIE Zeng-Qi, TIAN Lei-Lei, LIU Xiao-Dong, XU Jing-Sheng, MA Yu-Guang
    2006, 27(3):  510-514. 
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    We  fully optimized the trans-structures of PPV oligomer with biphenyl bridge using DFT/B3LYP method with Gaussian 98 software and gained the most rational geometry structure of ground state and electronic energy level. Then the absorption spectra data are calculated at ZINDO and TD-DFT levels of theory. We also analyzed the factors that different substituent groups connecting to the end of molecules impacted the frontier molecular orbitals and the energy gap. The results indicate that the PPV oligomer with biphenyl bridge is a cross form between two chains and tortuose derivative in the same chain. It reduces molecular symmetry and weakens π-π stacking effect among conjugated molecules in solid. This is perhaps the important factor that light-emitting diodes can increase fluorescence quantum efficiency.

    Studies on  Solubilization of Phospholipid Liposomes by Water-miscible Ionic Liquids
    SUN Chun-Yan, LI Di, WANG Mei-Jia, TANG Jiang, LIU Yang, LI Jing-Hong
    2006, 27(3):  515-518. 
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    AbstractThe effects of novel green solvents,ionic liquids(ILs),on the structures of phospholipid liposomes as model bio-membranes were studied.  The ILs-liposomes suspensions were characterized by turbidity,DSC and 31P NMR, and the results obtained demonstrate that  the interaction between water-miscible 1-n-alkyl-3-methylimidazolium ILs and  liposomes eventually led to the rupture of the liposome structures and the solubilization of the phospholipid components.  In the process,[Cnmim] cations played a crucial role in the solubilization of phospholipid liposomes,and the anion types and alkyl chain lengths also had influence on solubilizing properties of these ILs.  A possible mechanism involved in the ILs-induced solubilization of phospholipid liposomes was proposed.

    Mechanistic Studies on Mechanism of Propionic Acid Action in Elecroless Nickel Plating
    HU Guang-Hui, Wu Hui-Huang, YANG Fang-Zu
    2006, 27(3):  519-522. 
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    Propionic acid as an additive in electroless nickel plating will accelerate chemical deposition and raise P contents in the deposits.  In this work, the action mechanism of propionic acid in the electroless plating were studied by cyclic voltammetry and infrared reflection spectroscopy.  The voltammetric curves at various concentrations of propionic acid indicate that propionic acid will promote both cathodic Ni2＋ reduction and anodic NaH2PO2 oxidation.  According to the differences between the infrared reflection spectra of adsorbed propionic acid on Ni substrates and that of the adsorbed species when propionic acid co-exists with NaH2PO2 or NiSO4, it was proposed that the acceleration of chemical deposition was attributed to the formation of surface complexes of  propionic acid with NaH2PO2 and NiSO4,respectively.  Propionic acid could form intermolecular hydrogen bonds with NaH2PO2, which promotes splitting of P-H bond in the reductant and producing  PHO-2 intermediates, hence facilitates the oxidation of NaH2PO2.  At the same time, propionic acid is coordinated with Ni2＋ via   its  —OCO— group to form bridge complexes so as to promote NiSO4 reduction.  The accelerating oxidation of NaH2PO2 in turn helps the deposition of P, as a result, P contents in the deposits increase with accelerating NaH2PO2 oxidation. 

    Preparation of SERS Optical Fiber Sensor via Laser-induced Deposition of Ag Film on the Surface of Fiber Tip
    JIA Shao-Jie, XU Shu-Ping, ZHENG Xian-Liang, ZHAO Bing, XU Wei-Qing
    2006, 27(3):  523-526. 
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    A novel method of modifying the probe of SERS-optical sensor is described. By using laser-induced deposition and growth of Ag nanoparticles,we prepared a new type of Ag-deposited film with the appearance of annual rings on the fiber tip. A 6 cm-long silica fiber is immersed in the mixture of AgNO3 and citrate. A 514.5 nm laser with the power of 4.2 mW is used to reduce the Ag(Ⅰ) to Ag(0) and induced Ag(0) to deposit onto the fiber tip. SERS spectra of a probe molecule(BPENB) are used to monitor the deposition process. The optical and AFM images display the macro- and micro-appearance of Ag-deposited film. These results show that the laser-induced deposition is a simple and rapid method for modifying the probe of SERS-optical sensor. The Ag film with the proper thickness and roughness is prepared within only about 4.5 min. Moreover,the Ag deposition film prepared by this method shows not only easy reproduction but also remarkable SERS activity. The mechanism of the laser-induced Ag deposition onto the fiber tip was also discussed.

    Synthesis and Optical Properties of Semiconductor Nanocomposite Material ZnS/PMMA
    WANG Zhi-Peng, LI Xiao-Dong, LUO Qun, WONG Qi, ZHEN Zhen, LIU Xin-Hou
    2006, 27(3):  527-530. 
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    Nanocomposite materials have many peculiar optical characteristics and  quantum effect of the different nanoparticals in the matrix,such as optical amplification,photo absorbance fluorescence and nonlinear optical phenomena. And all of these materials have already exhibited immense application foreground,especially in the fields of optical apparatus and optical waveguide. Here the cubic nanocomposite materials ZnS/PMMA with good optical properties and machinability were synthesized by two methods of propolymerizing and swelling. TEM image was used to study ZnS nanoparticles in the PMMA matrix. Electron diffraction results show that the ZnS nanoparticles have a hexagonal structure. The ZnS nanoparticles growing process in the PMMA matrix at respective Zn2+ source of microgel(ZnP) and ZnCl2 was observed. The effect at different time on the preparation of these samples was measured by  using UV-Vis absorption and Fluorescence. The spectra show that PMMA have a new absorption peak at about 280 nm and strong fluorescence phenomenon when it mixed with ZnS.

    Theoretical Investigation of Interaction Between Di-nuclear Platinum Drug and DNA Duplex
    HUANG Su-Lan, HAO Lan, TAN Hong-Wei, CHEN Guang-Ju
    2006, 27(3):  531-534. 
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    Detailed studies of the geometrical and electrical configuration of the composite compound of the di-nuclear platinum compound ［{trans-PtCl(NH3)2}2(μ-NH2(CH2)nNH2)］2+and the 12-mer duplex d(ATATG*TACATAT)·d(ATATG*TACATAT) were performed by using the molecular mechanics and quantum chemistry methods. The investigating result shows that the coordinate bonds between Pt of the di-nuclear platinum composite compound and two N7′s of guanines in the DNA duplex are the most important interaction and hydrogen bond interactions are critical factors influencing the configuration of the composite compound. Based on the calculation results,we claim that little distortion of DNA binding the di-nuclear platinum complex may result in a significantly different antitumor activity from cis-platin.

    Theoretical Studies on SARS Coronavirus 3CL Proteinase and Its Inhibitor
    WANG Song, HUANG Xu-Ri, GAO Xue-Feng, ZHAO Xi, SUN Jia-Zhong
    2006, 27(3):  535-537. 
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    As a positive stranded RNA virus,SARS virus′s spread and replication are mainly determined by its inner six kinds of protein,including E protein,S protein,M protein,N protein,RNA polyprotein and proteinase.In the six ones,proteinase is closely related to the replication of the SARS virus,and so it is the best and the most important starting point when choosing medicine to kill virus. We docked ligand with receptor by means of Autodock program and simulated the molecular dynamic properties at SGI O3800 Operating Station through utilizing the Discover 3 modules of Insight II and analyzed the contour of proteinase pockets. Additiona-lly,we discussed interaction of subunits,hydrogen bonds,electronstatic and some hydrophobic effects,which provide an important reference for further studying the designing of medicine.

    Synthesis,Characterization and Catalytic Behavior of V-Si-β Molecular Sieves
    YU Ling, HE Hong-Yun, HE Chi-Jian, ZHU Hua-Yuan, WEN Jian-Jun, PANG Wen-Qin
    2006, 27(3):  538-542. 
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    V-β molecular sieves through isomorphous replacement of Si by V in zeolite β were successfully synthesized via hydrothermal procedure. The synthesis conditions were as follows: the molar chemical composition of the mixture: 60SiO2-xV2O5-y(TEA)2O-zH2O-wNH4F ( 1≤x≤6,y≥16,500≤z≤800,w≥5 ),reaction temperature 413 K,reaction time 12 d. The synthesized samples are characterized by XRD,IR,UV-Vis,TG,DTA and SEM. The results confirm that V-β molecular sieves contain a β phase of good species,and show the presence of V iron in the framework position. In the system the catalytic behavior of V-β molecular sieves in the hydroxylation of phenol with H2O2 as the oxidant was also investigated.

    Preparation of Modified Electrode of Multilayer Films of Polyoxometalat K17[Ce(P2Mo17O61)2] and Its Electrochemical Behavior
    WANG Li, HUANG Bing-Qiang, XIE Zhao-Xiong
    2006, 27(3):  543-545. 
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    The layer-by-layer assembly(LBL) is a technique  for production of the films in nanometer range. The modified electrode of multilayer films of polyoxometalate(POM) K17[Ce(P2Mo17O61)2]  and polyelectrolyte by the layer-by-layer assembly were prepared and investigated. The stable multilayer films were assembled by alternate adsorption of negatively charged POM and positively charged polyelectrolytes  from their aqueous dispersions. UV-Vis spectroscopy and cyclic voltammetry were used to monitor the regular growth of the multilayer films. The proposed novel immobilized method exhibited a good high sensitivity for the determination of electrocatalyst, which is important for practical applications.

    Delayed Feedback Control of Genesio Chaotic System
    HE Hong-Yan, CHENG Liang-Liang, GAO Feng-Xin, LI Qian-Shu
    2006, 27(3):  546-549. 
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    A method of time-delayed feedback control is applied to control Genesio chaotic system. Whether chaos is controlled or not relies on the values of controlled intensity and delayed time. The controlled results are different at different delayed time and different controlled intensities. In certain controlled direction,control is more easily realized. These results suggest that we could select appropriate controlled intensity,delayed time and controlled direction to obtain anticipative aim.

    Contents
    Studies on Tansport Mechanism of Photo-induced Charge Carrier on Nano-TiO2 Film Electrode Using Transient Photovoltage Technique
    ZHANG Qing-Lin, WANG De-Jun, WEI Xiao, ZHAO Qi-Dong, LIN Yan-Gong, YANG Min
    2006, 27(3):  550-552 . 
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    Transient photovoltage(PV) technique was applied to investigate the separation and the transport mechanism of the photo-induced charge carriers on nano-TiO2 film electrode. The positive PV transients were observed whenever the light was incident from the gauze platinum(top illumination) or the ITO electrode(bottom illumination). This implies that the photo-induced electrons always accumulate near the ITO. Simultaneously,it is found that under the singe pulse illumination,PV transient at bottom illumination needs a shorter time to reach its maximum than that at top illumination. This indicates that the photo-induced carriers are separated faster on TiO2/ITO interface than that in the bulk of the TiO2 film. These demonstrate the existence of the contact potential on the TiO2/ITO interface,with the downward band bending from the TiO2 to ITO,which may cause the excess carriers to be separated by drift. Under the repeated pulses illumination,the PV transients at top illumination remained unchanged,while those at bottom illumination changed significantly. This results from the trapping of the excess electrons on the TiO2/ITO interface.

    Spectroscopic Studies on Biosorption of Ag+
    XUE Ru, LIN Zhong-Yu, ZHENG Jian-Gong, WANG Qi, YAN Chang-Ming, CHEN Cui-Xue, XIE Jing, FU Jin-Kun
    2006, 27(3):  553-555. 
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    The biosorptive interaction of Ag+ with resting cell of Lactobacillus sp. strain A09 has been further studied on a molecular level by means of XPS,EDX,UV-Vis and FTIR techniques. The X-ray photoelectron spectroscopy(XPS) shows that the reductive ratio of the Ag+ to Ag0 by the A09 biomass reaches to about 54.5% for 3 d. The contain of amino acid residues in dry powder of the biomass such as cysteine,methionine,arginine and lysine,being capable of reducing the Ag+ to Ag0,are very small in quantity both cysteine and methionine are far less than 0.18%,and both arginine and lysine far less than 0.336%,via the analysis with quantitative energy-dispersive X-ray(EDX). The amount of the reducing sugars in the biomass is far larger than 2.71% analyzed by ultraviolet-visible spectrophotometry(UV-Vis). The chemical functional group on cell wass of the biomass such as the carboxylate anion of amino-acid residues seems to be the site for the Ag+ binding and the free aldehyde group of the hemiacetalic hydroxyl from reducing sugars,i.e. the hydrolysates of the polysaccharides from the cell wass,plays a protagonist in serving as the electron donor for reducing the Ag+ to Ag0,characterized by fourier transform infrared(FTIR) spectrophotometry.

    Reaction of Carotenoids with Nitrogen Dioxide Radical(NO·2)
    ZHAO Wen-En, HUANG Jin-Yong, WANG Wen-Feng, QIAN Su-Ping, YAO Si-De
    2006, 27(3):  556-558 . 
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    The interactions of carotenoids with NO·2 were investigated by pulse radiolysis. Optical traces show bleaching of the ground-state absorption of β-carotene,zeaxanthin and canthaxanthin at 450 nm,and bixin at 460—510 nm. The transient absorption spectrum shows that the positive absorption attributed to the formation of carotenoid addition radicals cannot be observed in the range of 600—700 nm. It is suggested that carotenoids undergo more readily electron transfer with NO·2 to yield the carotenoid radical cations. The rate constants for the reaction of β-carotene,zeaxanthin,bixin and canthaxanthin with NO·2 obtained are 1.6×108,2.41×108,5.41×107 and 1.75×107 mol/(L-1·s-1),respectively.

    Binding Kinetics Properties of Three Ru(Ⅱ) Complexes with Yeast-RNA
    JIANG Shang-Da, LI Shi-Yuan, CUI Meng-Chao, LIU Xia, WANG Ke-Zhi
    2006, 27(3):  559-561. 
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    The binding kinetics properties of three Ru(Ⅱ) complexes of ［Ru(bpy)2(dhipH3)］(ClO4)2,［(bpy)2Ru(eipcH)］(ClO4)2 and ［(bpy)2Ru(ebipcH2)Ru(bpy)2］(ClO4)4,where bpy=2,2′-bipyridine,dhipH3=3,4-dihydroxyphenyl-(imidazo［4,5-f］［1,10］phenanthroline),eipcH=N-ethyl-4-(imidazolo［4,5-f］-(1,10-phenanthrolin)-2-yl)carbazole,and ebipcH2=N-ethyl-4,7-bis(imidazolo［4,5-f］-(1,10-phenanthrolin)-2-yl)carbazole,with  yeast-RNA were investigated by monitoring the decays in absorbance for π-π* absorption peaks at 286 nm with binding time. The decay curves for the complexes were well fitting to biexponential decay functions with half-life times for rapidly-decayed components being 0.006,0.02 and 0.8 min,and those for slowly-decayed components being 0.7,4.2 and 103 min,respectively. The rapidly- and slowly-decayed components are probably due to electrostatic interaction and aromatic base stacking of the RNA with the Ru(Ⅱ) complexes,respectively. The results indicate that not only binuclear complexes but also mononuclear complexes can slowly bind to the RNA depending on the molecular structures of the complexes.

    Articles
    Synthesis of a Novel Second Order Nonlinear Optical Chromophore and Its Polyurethane Polymers
    ZU Feng-Hua, QIU Ling, CHEN Yu-Quan, DENG Xiao-Xu, ZHOU Jian-Gong, CHEN Qi-Shun, CAO Zhuang-Qi
    2006, 27(3):  562-566. 
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    A novel second-order NLO azo-chromophore containing thiophene conjugated bridge and TCF acceptor was synthesized and characterized by means of IR, UV, MS and  1H NMR. Two types of crosslinking polyurethane containing this chromophore were prepared, in which TEA and BPAN acted as the crosslinking agents, respectively. Second harmonic coefficient d33 values for the two polymers were measured by Marker-fringe method at 1 064 nm, they were 20.1 pm/V(chromophore number density is 2.21×1020 molecules/cm3) and 80.6 pm/V(chromophore number density is 0.91×1020 molecules/cm3), respectively. Polymer Ⅱ showed a thermal stability of 152 ℃, which was 71 ℃ higher than polymer Ⅰ.

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    FENG Jun, WANG Peng, LI Feng, HE Feng, ZHUO Ren-Xi
    2006, 27(3):  567-570. 
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    Enzymatic ring-opening polymerization of cyclic phosphate was achieved in this study.  NMR spectra experiments showed that the  polyphosphate prepared by CL-catalyzed ring-opening polymerization had hydroxy and phosphoric acid end-groups at both termini.  The influence of different reaction factors such as reaction temperature, enzyme concentration and polymerization time was studied.  Six phosphates with different alkyl groups were polymerized in bulk by using three different enzymes.  The result indicated that the length of alkyl groups made no marked influence on  Dp but affected the yield greatly.  The longer the length of alkyl groups, the stronger the lipophilicity of the polyphosphates is.  Porcine pancreas lipase(PPL) and candida rugosa lipase(CL) exhibited better activity than akaline phosphatase(AP) in this polymerization reaction.

    Synthesis and Charaterization of Crosslinkable Poly(MMA-co-GMA) and Its Application in Arrayed Waveguide Grating
    FEI Xu, FU Na, WANG Yao, HU Juan, CUI Zhan-Chen, ZHANG Da-Meng, MA Chun-Xiao, LIU Shi-Yong, YANG Bai
    2006, 27(3):  571-574. 
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    A novel crosslinkable poly(methyl methacrylate-co-glycidyl methacrylate)  synthesized and was determined by FTIR, 1H NMR, GPC,DSC and AFM. The polymers have an excellent film-forming capability and possess a high glass transition temperature after crosslinking.  The refractive index of the polymer can be adjusted between 1.483 and 1.588 at 1.55 μm by doping bisphenol A epoxy.  Because of three-dimensionally crosslinked structure, the birefringence of the polymers was very low. The arrayed waveguide grating, poly(MMA-co-GMA) acting as cladding and poly(MMA-co-GMA) doped bisphenol A epoxy acting as core layer, was fabricated by spin coating, using aluminum as mask and oxygen reactive ion etching.  And its optical properties were characterized.  The waveguide achived single-mode transmission and optical loss of the core layer was less than 3.0 dB/cm at 1.55 μm.

    Preparation of CaCO3/Chitosan Three-dimentinal  Composite Material via in-situ Precipitation
    HU Qiao-Ling, CHEN Zhong-Ke, CHEN Liang, SHEN Jia-Cong
    2006, 27(3):  575-578. 
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    A widely used inorganic compound in laboratory,CaCO3/chitosan composite with high performed and potential applicable prospects,was prepared by the method of in-situ precipitation. In this method the calcium ions were added into the solution of chitosan firstly and were dispersed homogeneously to attain the uniform solution. Then the uniform solution as the CaCO3/chitosan precursory solution was poured into a cylindrical glass mold,on the internal surface of which a chitosan membrane had been precipitated. Afterward the mold was soaked in the mixture of NaOH  and Na2CO3 aqueous solutions. Finally through the following proceedings,the three-dimensional composite in which the particles of calcium carbonate were dispersed was achieved in the experiment. XRD were carried out to determine the presence of the calcium carbonate. SEM was preformed to investigate the distributing regularity of calcium carbonate and the size of the calcium carbonate particle. It could be seen that the particles of orbicular were distributed orbicularly on the cross section and its size was about 5-10 μm. The mechanical properties of the composite were evaluated by three-point bending test. The bending strength enlarged firstly and then dropped with the increase of calcium carbonate′s mass fraction and the modulus decreased continuously.

    Monte Carlo Simulation of the Gelation Process of the Aqueous Polymer Weak Gel
    YANG Jian-Mao, CAO Xu-Long, ZHANG Kun-Ling, SONG Xin-Wang, QIU Feng, XU Yuan-Ze
    2006, 27(3):  579-582. 
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    To study the gelation process of weak gel and apply weak gel for the industrial practice of tertiary oil recovery,three dimensional Monte Carlo simulations were carried out to obtain the growth of average molecular weights and gel growth images.  It is found that the initial polymer concentration is critical for the gel formation.  The dismutation process of sol-gel groups is clearly observed.  The relationship between the speed of gelation and the concentration of crosslink agent was also simulated.  The predicted dependency of the gel time upon the concentration of crosslink agent is in good agreement with the experimental data of viscosity versus time.  Also,the polymer concentration effects agree well with  viscosity data.  The simulation correctly predicts that the concentration effect on crosslink reaction will be weaker at the higher polymer concentration.

    Contents
    Developement of Melt Agglomerate Structure in Conductive Polymer Composites Filled with Carbon Black
    WU Gang, ZHENG Qiang
    2006, 27(3):  583-585. 
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    The study on the correlation between time dependence of electrical resistivity and dynamic storage modulus for carbon black(CB) filled polymer composites was carried out. With the increase of the dynamic storage modulus(G′) as well as the normalized dynamic storage modulus(G′c /G′p),the volume resistivity(ρ) deceases with the  increase of annealing time beyond the Tm of the composites. It is believed that this phenomenon can be used for examining the development of agglomerate structure of filled composites and illustrating the micro-mechanism of the NTC behavior. It is assumed that melting treatment to CB filled composites results in a higher modulus and lower resistivity due to more even local dispersion of the particles and formation of perfect CB network structure within the matrix.

    Synthesis and Characterization of a Novel Sulfonated Polyimide Used as Proton Exchange Membrane
    DOU Zhi-Yu, LIU Chen-Guang,LI Xian-Feng,ZHAO Cheng-Ji, ZHONG Shuang-Ling, NA Hui
    2006, 27(3):  586-588. 
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    A series of sulfonated polyimides were synthesized by condensation of bis(p-hydroxylphenyl)-1,4,5,8-naphthalenetetracarboxylic di\|imide(NTDA) with various molar ratios of 3,3′-disulfonate-4,4′-dichlorodiphenylsulfone to 4,4′-dichlorodiphenyl\|sulfone. Both the monomers and the polymers were characterized by FTIR and 1H NMR. All the synthesized polymers have intrinsic viscosities above 0.70, which implies that the polymers have a high molecular weight. The DSC and TGA analysis of the polymers show that all of the polymers have good thermal stabilities. The polymers also  have a good solubility, and could be cast into tough membranes. Some properties of the polymer membranes were also studied.

    Studies on Cross-linked PPE π-π Stack Effect in Solid State
    WANG Wen-Zhong, HUANG Peng-Cheng
    2006, 27(3):  589-591. 
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    We synthesized oligo(p-phenyleneethynylene)s and oligo(p-phenyleneethynylene)s end-capped by vinyl by Sonogashira cross\|coupling reaction. Then we prepared cross-linked PPE with or without residue vinyl by radical polymerization or heat curing at 175\_280 ℃ of vinyl\|functionalized olgomers. Having investigated cross-linked PPE and oligomers by FTIR, WXRD and photoluminescence, we found that cross-linked PPE without residual vinyl destroys the main chain π-π stacking completely in solid state. Moreover, the wavelength of the strongest emission of these cross-linked PPE varies from 310 nm to 390 nm, so they can be used as purple/blue light\|emitting materials.

    Homogeneous Acetylation and Regioselectivity  of Cellulose in a New Ionic Liquid
    WU Jin, ZHANG Hao, ZHANG Jun, HE Jia-Song
    2006, 27(3):  592-594. 
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    Homogeneous acetylation of cellulose in 1-allyl-3-methyl-imidazolium chloride(AMIMCl) was carried out. Acetic anhydride and acetyl chloride were used as acetylating agents in the absence and presence of pyridine. The degree of substitution(DS) of the products and the distribution of substituents were determined by titration and 13C NMR techniques respectively. It was observed that acetyl chloride reacted faster than anhydride. Further,pyridine accelerated the reactions when anhydride was used as the acetylating agent,while it slowed down the reactions when acetyl chloride was used. An interesting distribution of  DSC-2 DSC-3 for substitutes was observed in the product with acetic anhydride/pyridine system.

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