反胶束法合成聚苯胺—无机物复合纳米粒子
|
摘要
由于纳米材料有许多与传统材料不同的物理、化学性质，并在电子、光学、机械、生物、医药、催化等领域显示出极大的应用价值，因而近二十年来受到了科学家们的广泛关注。特别是聚合物-无机复合纳米材料，由于有机-无机纳米复合材料同时具有有机聚合物的韧性、导电性、光电化学等方面的特性和无机物抗冲击、耐热、耐腐蚀的特性，是纳米科技领域内一项具有基础研究价值和广泛应用前景的重要课题。
本文采用三种不同的表面活性剂即阴离子型表面活性剂非离子型表面活性剂AOT(2-乙基己基琥珀酸钠)、Triton-X100或OP(聚氧乙烯烷基苯基醚)和阳离子型表面活性剂CTAB(十六烷基三甲基溴化铵)分别构建反胶束体系作为微反应器合成含有不同无机物内核(硫酸钡和氯化银)的聚苯胺-无机物复合纳米粒子，并在OP、AOT体系和CTAB体系中分别合成了具有一定微观结构的聚苯胺-二氧化钛复合纳米粒子，初步探讨了在反胶束水池中合成具有微观结构的纳米粒子的机理。
在AOT体系中合成聚苯胺-硫酸钡复合纳米粒子时，分别考察了搅拌因素和不同合成步骤对聚苯胺-硫酸钡尺寸及形态的影响，结果表明若想制备分布均匀，尺寸较小并且呈球形的复合纳米粒子应采用一步合成并在反应进行过程中伴随搅拌。
利用透射电子显微镜(TEM)、扫描电子显微镜(SEM)、红外光谱(IR)、紫外-可见光谱(UV-vis)、热失重分析(TGA)、X-射线衍射(XRD)和四探针电导率仪等测试手段对产物的形态、结构、结晶性、热稳定性和导电性等性质进行了一系列的表征。
Nanomaterials have been the focus of chemists and physicists due to their unusual application potentials in electronics, optics, mechanics, biology, medicine, catalysis, etc., among which polymer/inorganic nano-compsites are particularly challenging. The flexibilities and improved processability of polymers combined with inorganic components have particularly attractive modulus, transparency, surface hardness and heat resistance. Therefore, polymer/inorganic nanocomposite materials have been the focus of recent studies.
In this article, we aim to highlight the essential details of the method to synthesize PANI/inorganic nanocomposites. Anionic surfactant [sodium bis (2-ethylhexyl) sulfosuccinate (AOT)], nonionic surfactant (Triton-X100 or OP), and cationic surfactant [cetyltrimethyl-ammonium bromide (CTAB)] were used to form microreactors of the PANI/ inorganic nanocomposites. Triangle and sea urchin shaped polyaniline/TiO2 nanocomposites in AOT, OP, and CTAB system were observed respectively, and we proposed a hypothesis for the mechanism of nanoparticles' formation in reverse micelle.
Synthesis conditions such as stirring and experimental procedure were changed when PANI/BaSO4 was synthesized in AOT system. Then we draw a conclusion that we should stir the reactant and take the one step procedure to get monodisperse and spheroidal nanoparticles. It was also found that reverse micelle provide suitable spaces for the synthesis of nanocomposites with unique structure and morphologies.
These polyaniline-inorganic nanocomposites were characterized by transmission electron microscope (TEM), scanning electron microscope (SEM), infrared spectra (IR), Ultra Violet-visible spectra (UV-vis), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and electrical conductivities were measured by four-probe method.
本文采用三种不同的表面活性剂即阴离子型表面活性剂非离子型表面活性剂AOT(2-乙基己基琥珀酸钠)、Triton-X100或OP(聚氧乙烯烷基苯基醚)和阳离子型表面活性剂CTAB(十六烷基三甲基溴化铵)分别构建反胶束体系作为微反应器合成含有不同无机物内核(硫酸钡和氯化银)的聚苯胺-无机物复合纳米粒子，并在OP、AOT体系和CTAB体系中分别合成了具有一定微观结构的聚苯胺-二氧化钛复合纳米粒子，初步探讨了在反胶束水池中合成具有微观结构的纳米粒子的机理。
在AOT体系中合成聚苯胺-硫酸钡复合纳米粒子时，分别考察了搅拌因素和不同合成步骤对聚苯胺-硫酸钡尺寸及形态的影响，结果表明若想制备分布均匀，尺寸较小并且呈球形的复合纳米粒子应采用一步合成并在反应进行过程中伴随搅拌。
利用透射电子显微镜(TEM)、扫描电子显微镜(SEM)、红外光谱(IR)、紫外-可见光谱(UV-vis)、热失重分析(TGA)、X-射线衍射(XRD)和四探针电导率仪等测试手段对产物的形态、结构、结晶性、热稳定性和导电性等性质进行了一系列的表征。
Nanomaterials have been the focus of chemists and physicists due to their unusual application potentials in electronics, optics, mechanics, biology, medicine, catalysis, etc., among which polymer/inorganic nano-compsites are particularly challenging. The flexibilities and improved processability of polymers combined with inorganic components have particularly attractive modulus, transparency, surface hardness and heat resistance. Therefore, polymer/inorganic nanocomposite materials have been the focus of recent studies.
In this article, we aim to highlight the essential details of the method to synthesize PANI/inorganic nanocomposites. Anionic surfactant [sodium bis (2-ethylhexyl) sulfosuccinate (AOT)], nonionic surfactant (Triton-X100 or OP), and cationic surfactant [cetyltrimethyl-ammonium bromide (CTAB)] were used to form microreactors of the PANI/ inorganic nanocomposites. Triangle and sea urchin shaped polyaniline/TiO2 nanocomposites in AOT, OP, and CTAB system were observed respectively, and we proposed a hypothesis for the mechanism of nanoparticles' formation in reverse micelle.
Synthesis conditions such as stirring and experimental procedure were changed when PANI/BaSO4 was synthesized in AOT system. Then we draw a conclusion that we should stir the reactant and take the one step procedure to get monodisperse and spheroidal nanoparticles. It was also found that reverse micelle provide suitable spaces for the synthesis of nanocomposites with unique structure and morphologies.
These polyaniline-inorganic nanocomposites were characterized by transmission electron microscope (TEM), scanning electron microscope (SEM), infrared spectra (IR), Ultra Violet-visible spectra (UV-vis), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and electrical conductivities were measured by four-probe method.
引文
[1] 张立德，纳米材料，化学工业出版社，2001，第一版，42-44．
[2] Bernhard Wessling, Dispersion as the link between basic research and commercial applications of conductive polymers (polyaniline), Synth. Met., 1998,93,143-154.
[3] Barbeni M., et al., J. Chim.,1988, 9,67.
[4] 张池明，超微粒子的化学的特性，化学通报，1993，8，20．
[5] Bard A,Ber J,Bunsen-Ges. Phys. Chem.,1988, 92, 1194
[6] Q'Regan B,Gratzel M., A Low-cost High-efficiency Solar Cell Based on dye-sensitized Colloidal TiO2 Films, Nature, 1991, 353,737-740.
[7] Hagffeldt A., et al, Solar Energy Materials and Solar Cells, 1992, 92, 1194.
[8] 江龙，量子化尺寸纳米颗粒及其在生物体系中的作用，无机化学学报，2000，16，185-194．
[9] Richard L., Science News. 1994, 7, 24.
[10] Alan Sellinger, Pilar M.Weiss, Anh Nguyen, Yunfeng Lu, Roger A. Assink, Weiliang Gong,C.Jeffrey Brinker, Continiuous self-assembly of organic-inorganic nanocomposite coatings that mimic nacre, Nature, 998,394,256-260.
[11] Choi. C.S., Kim. Y.M., A study of the correlation between organic matrices and nanocomposite materials in oyster shell, Biomaterials, 2000, 21(3),213-222.
[12] Deng x., Hao J., Wang C., Preparation and mechanical properties of nanocomposites of poly (D, L-Lactide) with Ca-deficient hydroxyapatite nanocrystals, Biomaterials, 2001,22 (21), 2867-2873.
[13] 顾群，吴大诚，易国祯，张国耀，杨宇，吴立衡，聚醚酯／蒙脱土复合材料的结晶动力学和结晶形态，高等学校化学学报，1999，20(2)，324-326．
[14] 张国耀，易国祯，吴立衡，徐翔，宋青，杨宇，金剑，钟淑芳，漆宗能，聚对苯二甲酸乙二酯／蒙脱土纳米复合材料的制备和性能，高分子
学报，1999，3，309-314．
[15] Shouji, Eiichi Buttry, Daniel A., New Organic-Inorganic Nanocomposite Materials for Energy Storage Applications, Langmuir, 1999,15(3), 669.
[16] Li, Z. F., Ruckenstein, E., Intercalation of Conductive Polyaniline in the Mesostructured V_2O_5, Langmuir; 2002, 18(18), 6956-6961.
[17] Yanjing Liu, Anbo Wang, Richard Claus, Molecular Self-Assembly of TiO_2/Polymer Nanocomposite Films, J. Phys. Chem. B., 1997, 101, 1385-1388.
[18] Wessling, B., Dispersion as the link between basic research and commercial applications of conductive polymers (polyaniline), Synth. Met., 1998, 93, 143-154.
[19] Nguyen M.T., Diaz A.F., A novel method for the preparation of magnetic nanoparticles in a polypyrrole powder. Adv. Mater., 1994,6(11),858-860.
[20] Bidan G., Jarjayes O., Fruchart J.M., et al., New nanocomposites based on 'tailor dressed' magnetic particles in a polypyrrole matrix. Adv. Mater., 1994,6(2),152-155.
[21] Jarjayes O., Fries P.H., Bidan G., New nanocomposites of polypyrrole inducing γ-Fe_2O_3 particles: electrical and magnetic characterization. Synth. Met., 1995,69,343-344.
[22] Jarjayes O., Fries P.H., Bidan G., Magnetic properties of fine maghnite particles in an electroconducting polymer matrix, J. Magn. Magn. Mater., 1994,137,205-218.
[23] Jarjayes O., Fries P.H., Bidan G., Mossbauer investigation of γ-Fe_2O_3 nanocrystals embedded in polypyrrole. J. Magn. Magn. Mater., 1994, 138,115-122.
[24] Wan M.X., Zhou W.X., Li J.C., Composite of polyaniline containing iron oxides with nanometer size, Synth. Met., 1996,78,27-31.
[25] Wan M.X., Li J.C., Synthesis and electrical-magnetic properties of polyaniline composites. J. Polym. Sci: Part A, 1998,36,2799-2805.
[26] Tang B.Z., Geng Y.H., Lam J. et al., Processible nanostructured material with electrical conductivity and magnetic susceptibility: preparation and properties of maghemite/polyaniline nanocomposible
films. Chem. Mater., 1999,11,1581-1589.
[27] Butterworth M.D., Armes S.P., Simpson A.W., Synthesis of poly (Pyrrole)-silica-magnetite nanocomposites panicles. J. Chem. Soc. Chem. Commun., 1994,2129-2130.
[28] Butterworth M.D., Bell S.A., Armes S.P., Synthesis and characterization of polypyrrole-magnetite-silica particles. J. Colloid. Interface. Sci., 1996, 183, 91-99.
[29] Zhang P., Yang Z.H., Wang D.J., et al., Electrochemical deposition and photovoltatic properties of nano-Fe_2O_3-incorporated polypyrrole films. Synth. Met., 1997,84,165-166.
[30] Kryszewski M., Jeszka J.K., Nanostructured conducting polymer composites-superparamagnetic particles in conducting polymers. Synth. Met., 1998,94,99-104.
[32] K.K.Lee, J.M.Vohs, N.J.DiNardo, HREELS study of ultra-thin polyaniline films grown on Cu (110) by vapor deposition of aniline tetramers, Synth. Met., 2000,113,231-236.
[33] Suprakas Sinha Ray. Mukul Biswas, Water-dispersible conducting nanocomposites of polyaniline and poly (N-vinylcarbazole) with nanodimensional zirconium dioxide, Synth. Met., 2000,108,231-236.
[34] N.I.Kovtyukhova, A.D.Gorchinskiy, C.Waraksa, Self-assembly of nanostructured composite ZnO/polyaniline films, Materials Science and Engineering B, 2000,69-70,424-430.
[35] G.G.Wu, D.C.DeGroot, H.O.Marcy, J.L.Schindler, C.R.Kannewurf, Y.J.Liu, W. Hirpo, M.G.Kanatzidis, Redox intercalative polymerization of aniline in V_2O_5 xerogel. The postintercalative intralamellar polymer growth in polyaniline/metal oxide nanocomposites is facilitated by molecular oxygen, Chem. Mater., 1996,8,1992-2004.
[36] Chin-Lin Huang, Richard E. Partch, Egon Matijevic, Coating of uniform inorganic particles with polymers Ⅱ polyaniline on copper
oxide, J. Colloid. Interface. Sci., 1995,170,275-283.
[37] Mukul Biswas, Suprakas Sinha Ray, Yunping Liu, Water dispersible conducting nanocomposites of poly (N-vinylcarbazole), polypyrrole and polyaniline with nanodimensional manganese (Ⅳ) oxide, Synth.Met., 1999,105,99-105.
[38] Shi-Jian Su, Noriyuki Kuramoto, Processable polyailine-titanium dioxide nanocomposite: effect of titanium dioxide on the conductivity,Synth. Met., 2000,114,147-153.
[39] 黄怀国，郑志新，罗瑾，张红平，吴玲玲，林仲华，TiO_2-聚苯胺复合膜的光电化学，电化学，2001，7(1)，102-108．
[40] 刘少琼，于黄中，黄河，熊予莹，TiO_2纳米微粒对聚苯胺性能的影响，高等学校化学学报，2002，23(1)，161-163．
[41] S.P. Armes, S.Gottesfeld, J.G.Beery, F. Garzon, S.F.Agnew,Conducting polymer-colloidal silica composites, Polymer, 1991,32,2325-2330.
[42] S.H.Jang, M.G.Han, S.S.Im, Preparation and characterization of conductive polyaniline/silica hybrid composites prepared by sol-gel process, Synth. Met., 2000,110,17-23.
[43] 吴秋菊，薛志坚，漆宗能，王佛松，具有伸展链构象聚苯胺／蒙脱土混杂纳米复合物的合成与表征，高分子学报，1999，10，551-556．
[44] 蒋殿录，翁永良，童汝亨，聚苯胺／膨润土纳米复合材料的合成与表征，物理化学学报，1999，1，69-72．
[45] 邬润德，童筱莉，周安安，SOL-GEL法制有机聚合物／无机纳米粒子复合材料，浙江工业大学学报，2000，28，288-292．
[46] 李曦，孙江勤，张超灿，溶胶-凝胶法制备有机-无机杂化纳米级功能材料，湖北华工，2000，17，5-7．
[47] Kerr. T. A., Wu. H., Nazar. L. F., Concurrent Polymerization and Insertion of Aniline in Molybdenum Trioxide: Formation and Properties of a [Poly (aniline)]_(0.24)MoO_3 Nanocomposite, Chem. Mater., 1996, 8, 2005-2015.
[48] Kanatzidis. M. G., Wu. C. G., Marcy. H. O., Kannewurf. C. R., Conductive-polymer bronzes. Intercalated polyaniline in vanadium
oxide xerogels, d. Am. Chem. Soc., 1989,111, 4139-4142.
[49] Liu. Y., Wang. A., Claus. R., Molecular Self-Assembly of TiO_2/Polymer Nanocomposite Films, J. Phys. Chem. B, 1997, 101,1385-1387.
[50] Su, S. J., Kuramoto, N., Processable polyaniline-titanium dioxide nanocomposites: effect of titanium dioxide on the conductivity, Synth. Met., 2000, 114, 147-153.
[51] Chen. S. A., Fang. W. G., Electrically conductive polyaniline-poly (vinyl alcohol) composite films: physical properties and morphological structures, Macromolecules, 1991,24, 1242-1248.
[52] Susumu Shiojiri, Takayuki Hirai, Isao Komasawa, Preparation and photocatalytic reactions of titanium dioxide ultrafine panicles in reverse micellar systems, Journal of Chemical Engineering of Japan, 1997,30,137-145.
[53] 周海成，徐健，李亚栋，PbSO4纳米片晶的微乳法制备与自组装，高等学校化学学报，2002，23，1645-1647．
[54] F. Debuigne, L. Jeunieau, M. Wiame, J.B.Nagy, Synthsis of Organic Nanoparticles in Different W/O Microemulsions, Langmtdr, 2000, 16,7605-7611.
[55] L.M. Gan, E.H. Zhang, H.S.O. Chan. C.H. Chew, Preparation of conducting polyaniline-coated barium sulfate nanoparticles in inverse microemulsions, Mater. Chem. Phys., 1995,40,94-98.
[56] 徐相凌，殷亚东，葛学武，微乳液聚合研究进展，高等学校化学学报，1999，3，478．
[57] Stamatis H., Xenakis A., Kolisis F. N.. Bioorganic Reactions in microemulsions: the case of lipases, Biotechnology Advances, 1999, 17,293-318.
[58] Goto M., Ono T., Nakashio F., et al., Design of surfactants suitable for protein extraction by reversed micelles, Biotechnol. Bioeng., 1997.54(1), 26～32.
[59] 陆强，李宽宏，施亚钧，反胶束萃取蛋白质技术的新进展，化工进展，1995，51(1)，25-28．
[60] 赵国玺，表面活性剂物理化学，北京，北京大学出版社，1991，
194-406.
[61] 虞炳钧，发酵产物后处理技术新动态，微尘物学通报 1992，19(1)，39-44．
[62] Luisi P. L., Bommer F. J., Pellegrini A., et al., Micellar Solubilization of Proteins in Aprotic Solvents and their spectroscopic characteri-zation, Helv. Chim Acta., 1979, 62(3), 740-753.
[63] Magid L., Walde P., Zampieri G., et al., Research report on proteins in reverse micelles. Structural aspect and enzymology, Colloids and Surfaces,. 1988, 30(1), 193-207.
[64] 陆强，李宽宏，施亚钧，用反胶束萃取法提取与分离蛋白质和酶，生物工程进展，1992，12(6)，12-16．
[65] 许建和，胡英．生物转化中的有机介质系统(综述)，．化学世界，1991，32(7)，290-293．
[66] Srivastava R.C., Madamwar D.B., Vyas V.V., Activation of enzymes by reversed micelles, Biotechnol. Bioeng., 1987, 29, 901-902.
[67] Prazeres D.M.F., Garcia F.A.P., Cabral J.M.S.. Kinetics and stability of a chromolacterium viscosum lipase in reversed micellar and aqueous media, J. Chem. Tech. Biotechnol., 1992, 53,159-164.
[68] Misiorowski R.L., Wells M.A., Activity of phospholipase A2 in reversed micelles of phosphatidylcholine in diethyl ether. Effect of water and cations, Biochem., 1974, 13, 4921-4927.
[69] Iarur A.J., Ying J.Y.. Reversr microemulsion synthesis of nanostructured complex oxides for catalytic combustion, Nature, 2000, 403, 65-67.
[70] Boutonnet M., Kizhig J., Stenius P., The preparation of nomodisperse colloidal metal particles from microemulsion, Colloids and Surfaces, 1982, 5,209-225.
[71] Sato H., Asaji N., Komasawa I., A population balance approach for particle coagulation in reverse micelles, Ind. Eng. Chem. Res., 2000, 39, 328-334.
[72] Bandyopadhyaya R., Kumar R., Gandhi K. S., Simulation of precipitation reactions in reverse micelle, Langmuir. 2000, 16, 7139-7149.
[73] Lisiecki I., Pileni M.P., Synthsis of copper metallic clusters using reverse micelles as microreactors, J. Am. Chem. Soc., 1993, 115,887.
[74] 成国祥，沈锋，张仁伯等，反相胶束微反应器及其制备纳米微粒的研究进展，化学通报，1997，3，14．
[75] Lizhong Feng, K. Y. Simon Ng, In situ kinetic studies of microemulsion polymerizations of styrene and methyl methacrylate by Raman spectroscopy, Macromolecules, 1990, 23(4), 1048-1053.
[76] Holdcroft S., Guiliet E., Microemulsion polymerization of styrene:A study using pulsed laser initiation, J.. Polym. Sci. Part A: Polym. Chem., 1990, 28,1823.
[77] Atik S. S., Thomas J. K., Polymerized microemulsions, J. Am. Chem. Soc., 1981, 103 4279-4280.
[78] Johnson P. L., Gulari E., Characteristics of Micromulsuin Polymerized Stysene with Water-soluble Versus Oil-soluble Initiators, J. Polym. Sci. Part A.' Polym. Chem., 1984, 22, 3967-3982.
[79] Gan L. M., Chew C. H., Lee K. C., Formation of polystyrene nanoparticles in ternary cationic microemulsions, Polymer, 1994. 35, 2659.
[80] Gan L. M., Lee K. C., Chew C. H., et al, Growth of poly (methyl methacrylate) particles in three-component cationic microemulsions, or. Polym. Sci., Part A: Polym. Chem., 1995.33.1161
[81] Gan L. M., lian N., Chew C. H., Li G. Z., Polymerization of Styrene in a Winsor I-like System, Langmuir, 1994, 10,2197-2201.
[82] Loh S.E., Gan L.M., Chew C. H. et al, Polemerization of methyl mathacrylate in winsor I-like system, J. Macromol. Sci., Pure ,Appl. Chem., 1996, A33, 371-384.
[83] 刘国军，王国昌，嵌段共聚物纳米结构材料，何天白，胡汉杰。海外高分子科学的新进展，1997年，第二版，39-50．
[84] Kortan A.R., Hull R., Opila R.L.. et al., Nucleation and Growth CdSe on ZnS Quantum Crystallite Seeds, and Vice verse, in Inverse Micelle Media. J. Am. Chem. Soc.. 1990,112.1317-1322.
[85] 李文华，王洪鉴，刘明翠等，W／O微孔液中Au／Fe_2O_3超微粒的制备，山东师大学报，1997，12(4)。406-410．
[86] Ogawa S., Kai Hu, Fu-Ren F. Fan, et al., Photoelectrochemistry of films of quantum size lead sulfide particles incorporated in self-assembled monolayers on gold, J. Phys Chem. B, 1997, 101, 5707-5711.
[87] Zou B.S., Little R.B., Wang J.P., et al., Effect of different capping environments on the optical Properties of CdS nanoparticles in reverse micelles, J. Inter. Quant. Chem., 1999, 75,439-450.
[88] Andrey J. Zarur and Jackie Y. Ying, Reverse microemulsion synthesis of nanostructured cornplex oxide for catalytic combustion, Nature, 2000, 403, 65-67.
[89] Shi-Jian Su, Noriyuki Kuramoto, Processable polyaniline-titanium dioxide nanocomposites: effect of titanium dioxide on the conductivity, Synth. Met., 2000,114,147-153.
[90] Alan G.Macdiarmid, Arthur Epstein, Secondary doping in polyaniline, Synth. Met.,1995,69,85-92.
[91] 刘成站，东北师范大学硕士学位论文，2001．
[92] Tzou K., Gregory R. V., Kinetic Study of the Chemical Polymerization of Aniline in Aqueous Solutions, Synth. Met, 1992,47,267.
[93] P.J.Kinlen, D.C.Silverman, C.R.Jeffreys, Corrosion protection using polyaniline coating formulations, Synth. Met, 1997,84-86, 1327.
[94] Li J. Kham T.M., Highly conductive solid polymer electrolytes prepared by blending high molecular weight poly (ethylene oxide), poly (2- or 4-vinylpyridine), and lithium perchlorate, Macromolecules, 1993, 26(17), 4544.
[95] 孟繁涛，东北师范大学硕士学位论文，1999．
[96] 刘景林，东北师范大学硕士学位论文，1997．
[97] 闫云，东北师范大学硕士学位论文，2000．
[98] Hailin Fan, Ying Chu, et al., Lipase-catalyzed synthesis of monoglcerides by hydrolysis of Sogban oil in AOT/iso-octane reversed micelles, Annals of the New York academy of sciences enzyme engineering. XIV, December 13,1998,267-272.
[99] 张薇，东北师范大学硕士学位论文，1998．
[100] 刘景林，史月华，褚莹等，AEOT／异新烷／水反胶束体系对血红蛋白的提取，高等学校化学学报，1999，120，1122-1124．
[101] 褚莹，孟繁涛，吴子尘等，反胶团法提取细胞色素C，东北师大学报，1994，2，133．
[102] 褚莹，纪建业，马占芳等，反胶团相转移法提纯酵母脂肪酶，高等学校化学学报，1997，10，1695-1697．
[103] 冯琳，东北师范大学硕士学位论文，2000。
[104] 陈悦，东北师范大学硕士学位论文，2001．
[105] Jinsong Tang, Xiabin Jing, Baochen Wang and Fosong Wang, Infrared spectra of soluble polyaniline, Synth. Met., 1988, 24,231-238.
[2] Bernhard Wessling, Dispersion as the link between basic research and commercial applications of conductive polymers (polyaniline), Synth. Met., 1998,93,143-154.
[3] Barbeni M., et al., J. Chim.,1988, 9,67.
[4] 张池明，超微粒子的化学的特性，化学通报，1993，8，20．
[5] Bard A,Ber J,Bunsen-Ges. Phys. Chem.,1988, 92, 1194
[6] Q'Regan B,Gratzel M., A Low-cost High-efficiency Solar Cell Based on dye-sensitized Colloidal TiO2 Films, Nature, 1991, 353,737-740.
[7] Hagffeldt A., et al, Solar Energy Materials and Solar Cells, 1992, 92, 1194.
[8] 江龙，量子化尺寸纳米颗粒及其在生物体系中的作用，无机化学学报，2000，16，185-194．
[9] Richard L., Science News. 1994, 7, 24.
[10] Alan Sellinger, Pilar M.Weiss, Anh Nguyen, Yunfeng Lu, Roger A. Assink, Weiliang Gong,C.Jeffrey Brinker, Continiuous self-assembly of organic-inorganic nanocomposite coatings that mimic nacre, Nature, 998,394,256-260.
[11] Choi. C.S., Kim. Y.M., A study of the correlation between organic matrices and nanocomposite materials in oyster shell, Biomaterials, 2000, 21(3),213-222.
[12] Deng x., Hao J., Wang C., Preparation and mechanical properties of nanocomposites of poly (D, L-Lactide) with Ca-deficient hydroxyapatite nanocrystals, Biomaterials, 2001,22 (21), 2867-2873.
[13] 顾群，吴大诚，易国祯，张国耀，杨宇，吴立衡，聚醚酯／蒙脱土复合材料的结晶动力学和结晶形态，高等学校化学学报，1999，20(2)，324-326．
[14] 张国耀，易国祯，吴立衡，徐翔，宋青，杨宇，金剑，钟淑芳，漆宗能，聚对苯二甲酸乙二酯／蒙脱土纳米复合材料的制备和性能，高分子
学报，1999，3，309-314．
[15] Shouji, Eiichi Buttry, Daniel A., New Organic-Inorganic Nanocomposite Materials for Energy Storage Applications, Langmuir, 1999,15(3), 669.
[16] Li, Z. F., Ruckenstein, E., Intercalation of Conductive Polyaniline in the Mesostructured V_2O_5, Langmuir; 2002, 18(18), 6956-6961.
[17] Yanjing Liu, Anbo Wang, Richard Claus, Molecular Self-Assembly of TiO_2/Polymer Nanocomposite Films, J. Phys. Chem. B., 1997, 101, 1385-1388.
[18] Wessling, B., Dispersion as the link between basic research and commercial applications of conductive polymers (polyaniline), Synth. Met., 1998, 93, 143-154.
[19] Nguyen M.T., Diaz A.F., A novel method for the preparation of magnetic nanoparticles in a polypyrrole powder. Adv. Mater., 1994,6(11),858-860.
[20] Bidan G., Jarjayes O., Fruchart J.M., et al., New nanocomposites based on 'tailor dressed' magnetic particles in a polypyrrole matrix. Adv. Mater., 1994,6(2),152-155.
[21] Jarjayes O., Fries P.H., Bidan G., New nanocomposites of polypyrrole inducing γ-Fe_2O_3 particles: electrical and magnetic characterization. Synth. Met., 1995,69,343-344.
[22] Jarjayes O., Fries P.H., Bidan G., Magnetic properties of fine maghnite particles in an electroconducting polymer matrix, J. Magn. Magn. Mater., 1994,137,205-218.
[23] Jarjayes O., Fries P.H., Bidan G., Mossbauer investigation of γ-Fe_2O_3 nanocrystals embedded in polypyrrole. J. Magn. Magn. Mater., 1994, 138,115-122.
[24] Wan M.X., Zhou W.X., Li J.C., Composite of polyaniline containing iron oxides with nanometer size, Synth. Met., 1996,78,27-31.
[25] Wan M.X., Li J.C., Synthesis and electrical-magnetic properties of polyaniline composites. J. Polym. Sci: Part A, 1998,36,2799-2805.
[26] Tang B.Z., Geng Y.H., Lam J. et al., Processible nanostructured material with electrical conductivity and magnetic susceptibility: preparation and properties of maghemite/polyaniline nanocomposible
films. Chem. Mater., 1999,11,1581-1589.
[27] Butterworth M.D., Armes S.P., Simpson A.W., Synthesis of poly (Pyrrole)-silica-magnetite nanocomposites panicles. J. Chem. Soc. Chem. Commun., 1994,2129-2130.
[28] Butterworth M.D., Bell S.A., Armes S.P., Synthesis and characterization of polypyrrole-magnetite-silica particles. J. Colloid. Interface. Sci., 1996, 183, 91-99.
[29] Zhang P., Yang Z.H., Wang D.J., et al., Electrochemical deposition and photovoltatic properties of nano-Fe_2O_3-incorporated polypyrrole films. Synth. Met., 1997,84,165-166.
[30] Kryszewski M., Jeszka J.K., Nanostructured conducting polymer composites-superparamagnetic particles in conducting polymers. Synth. Met., 1998,94,99-104.
[32] K.K.Lee, J.M.Vohs, N.J.DiNardo, HREELS study of ultra-thin polyaniline films grown on Cu (110) by vapor deposition of aniline tetramers, Synth. Met., 2000,113,231-236.
[33] Suprakas Sinha Ray. Mukul Biswas, Water-dispersible conducting nanocomposites of polyaniline and poly (N-vinylcarbazole) with nanodimensional zirconium dioxide, Synth. Met., 2000,108,231-236.
[34] N.I.Kovtyukhova, A.D.Gorchinskiy, C.Waraksa, Self-assembly of nanostructured composite ZnO/polyaniline films, Materials Science and Engineering B, 2000,69-70,424-430.
[35] G.G.Wu, D.C.DeGroot, H.O.Marcy, J.L.Schindler, C.R.Kannewurf, Y.J.Liu, W. Hirpo, M.G.Kanatzidis, Redox intercalative polymerization of aniline in V_2O_5 xerogel. The postintercalative intralamellar polymer growth in polyaniline/metal oxide nanocomposites is facilitated by molecular oxygen, Chem. Mater., 1996,8,1992-2004.
[36] Chin-Lin Huang, Richard E. Partch, Egon Matijevic, Coating of uniform inorganic particles with polymers Ⅱ polyaniline on copper
oxide, J. Colloid. Interface. Sci., 1995,170,275-283.
[37] Mukul Biswas, Suprakas Sinha Ray, Yunping Liu, Water dispersible conducting nanocomposites of poly (N-vinylcarbazole), polypyrrole and polyaniline with nanodimensional manganese (Ⅳ) oxide, Synth.Met., 1999,105,99-105.
[38] Shi-Jian Su, Noriyuki Kuramoto, Processable polyailine-titanium dioxide nanocomposite: effect of titanium dioxide on the conductivity,Synth. Met., 2000,114,147-153.
[39] 黄怀国，郑志新，罗瑾，张红平，吴玲玲，林仲华，TiO_2-聚苯胺复合膜的光电化学，电化学，2001，7(1)，102-108．
[40] 刘少琼，于黄中，黄河，熊予莹，TiO_2纳米微粒对聚苯胺性能的影响，高等学校化学学报，2002，23(1)，161-163．
[41] S.P. Armes, S.Gottesfeld, J.G.Beery, F. Garzon, S.F.Agnew,Conducting polymer-colloidal silica composites, Polymer, 1991,32,2325-2330.
[42] S.H.Jang, M.G.Han, S.S.Im, Preparation and characterization of conductive polyaniline/silica hybrid composites prepared by sol-gel process, Synth. Met., 2000,110,17-23.
[43] 吴秋菊，薛志坚，漆宗能，王佛松，具有伸展链构象聚苯胺／蒙脱土混杂纳米复合物的合成与表征，高分子学报，1999，10，551-556．
[44] 蒋殿录，翁永良，童汝亨，聚苯胺／膨润土纳米复合材料的合成与表征，物理化学学报，1999，1，69-72．
[45] 邬润德，童筱莉，周安安，SOL-GEL法制有机聚合物／无机纳米粒子复合材料，浙江工业大学学报，2000，28，288-292．
[46] 李曦，孙江勤，张超灿，溶胶-凝胶法制备有机-无机杂化纳米级功能材料，湖北华工，2000，17，5-7．
[47] Kerr. T. A., Wu. H., Nazar. L. F., Concurrent Polymerization and Insertion of Aniline in Molybdenum Trioxide: Formation and Properties of a [Poly (aniline)]_(0.24)MoO_3 Nanocomposite, Chem. Mater., 1996, 8, 2005-2015.
[48] Kanatzidis. M. G., Wu. C. G., Marcy. H. O., Kannewurf. C. R., Conductive-polymer bronzes. Intercalated polyaniline in vanadium
oxide xerogels, d. Am. Chem. Soc., 1989,111, 4139-4142.
[49] Liu. Y., Wang. A., Claus. R., Molecular Self-Assembly of TiO_2/Polymer Nanocomposite Films, J. Phys. Chem. B, 1997, 101,1385-1387.
[50] Su, S. J., Kuramoto, N., Processable polyaniline-titanium dioxide nanocomposites: effect of titanium dioxide on the conductivity, Synth. Met., 2000, 114, 147-153.
[51] Chen. S. A., Fang. W. G., Electrically conductive polyaniline-poly (vinyl alcohol) composite films: physical properties and morphological structures, Macromolecules, 1991,24, 1242-1248.
[52] Susumu Shiojiri, Takayuki Hirai, Isao Komasawa, Preparation and photocatalytic reactions of titanium dioxide ultrafine panicles in reverse micellar systems, Journal of Chemical Engineering of Japan, 1997,30,137-145.
[53] 周海成，徐健，李亚栋，PbSO4纳米片晶的微乳法制备与自组装，高等学校化学学报，2002，23，1645-1647．
[54] F. Debuigne, L. Jeunieau, M. Wiame, J.B.Nagy, Synthsis of Organic Nanoparticles in Different W/O Microemulsions, Langmtdr, 2000, 16,7605-7611.
[55] L.M. Gan, E.H. Zhang, H.S.O. Chan. C.H. Chew, Preparation of conducting polyaniline-coated barium sulfate nanoparticles in inverse microemulsions, Mater. Chem. Phys., 1995,40,94-98.
[56] 徐相凌，殷亚东，葛学武，微乳液聚合研究进展，高等学校化学学报，1999，3，478．
[57] Stamatis H., Xenakis A., Kolisis F. N.. Bioorganic Reactions in microemulsions: the case of lipases, Biotechnology Advances, 1999, 17,293-318.
[58] Goto M., Ono T., Nakashio F., et al., Design of surfactants suitable for protein extraction by reversed micelles, Biotechnol. Bioeng., 1997.54(1), 26～32.
[59] 陆强，李宽宏，施亚钧，反胶束萃取蛋白质技术的新进展，化工进展，1995，51(1)，25-28．
[60] 赵国玺，表面活性剂物理化学，北京，北京大学出版社，1991，
194-406.
[61] 虞炳钧，发酵产物后处理技术新动态，微尘物学通报 1992，19(1)，39-44．
[62] Luisi P. L., Bommer F. J., Pellegrini A., et al., Micellar Solubilization of Proteins in Aprotic Solvents and their spectroscopic characteri-zation, Helv. Chim Acta., 1979, 62(3), 740-753.
[63] Magid L., Walde P., Zampieri G., et al., Research report on proteins in reverse micelles. Structural aspect and enzymology, Colloids and Surfaces,. 1988, 30(1), 193-207.
[64] 陆强，李宽宏，施亚钧，用反胶束萃取法提取与分离蛋白质和酶，生物工程进展，1992，12(6)，12-16．
[65] 许建和，胡英．生物转化中的有机介质系统(综述)，．化学世界，1991，32(7)，290-293．
[66] Srivastava R.C., Madamwar D.B., Vyas V.V., Activation of enzymes by reversed micelles, Biotechnol. Bioeng., 1987, 29, 901-902.
[67] Prazeres D.M.F., Garcia F.A.P., Cabral J.M.S.. Kinetics and stability of a chromolacterium viscosum lipase in reversed micellar and aqueous media, J. Chem. Tech. Biotechnol., 1992, 53,159-164.
[68] Misiorowski R.L., Wells M.A., Activity of phospholipase A2 in reversed micelles of phosphatidylcholine in diethyl ether. Effect of water and cations, Biochem., 1974, 13, 4921-4927.
[69] Iarur A.J., Ying J.Y.. Reversr microemulsion synthesis of nanostructured complex oxides for catalytic combustion, Nature, 2000, 403, 65-67.
[70] Boutonnet M., Kizhig J., Stenius P., The preparation of nomodisperse colloidal metal particles from microemulsion, Colloids and Surfaces, 1982, 5,209-225.
[71] Sato H., Asaji N., Komasawa I., A population balance approach for particle coagulation in reverse micelles, Ind. Eng. Chem. Res., 2000, 39, 328-334.
[72] Bandyopadhyaya R., Kumar R., Gandhi K. S., Simulation of precipitation reactions in reverse micelle, Langmuir. 2000, 16, 7139-7149.
[73] Lisiecki I., Pileni M.P., Synthsis of copper metallic clusters using reverse micelles as microreactors, J. Am. Chem. Soc., 1993, 115,887.
[74] 成国祥，沈锋，张仁伯等，反相胶束微反应器及其制备纳米微粒的研究进展，化学通报，1997，3，14．
[75] Lizhong Feng, K. Y. Simon Ng, In situ kinetic studies of microemulsion polymerizations of styrene and methyl methacrylate by Raman spectroscopy, Macromolecules, 1990, 23(4), 1048-1053.
[76] Holdcroft S., Guiliet E., Microemulsion polymerization of styrene:A study using pulsed laser initiation, J.. Polym. Sci. Part A: Polym. Chem., 1990, 28,1823.
[77] Atik S. S., Thomas J. K., Polymerized microemulsions, J. Am. Chem. Soc., 1981, 103 4279-4280.
[78] Johnson P. L., Gulari E., Characteristics of Micromulsuin Polymerized Stysene with Water-soluble Versus Oil-soluble Initiators, J. Polym. Sci. Part A.' Polym. Chem., 1984, 22, 3967-3982.
[79] Gan L. M., Chew C. H., Lee K. C., Formation of polystyrene nanoparticles in ternary cationic microemulsions, Polymer, 1994. 35, 2659.
[80] Gan L. M., Lee K. C., Chew C. H., et al, Growth of poly (methyl methacrylate) particles in three-component cationic microemulsions, or. Polym. Sci., Part A: Polym. Chem., 1995.33.1161
[81] Gan L. M., lian N., Chew C. H., Li G. Z., Polymerization of Styrene in a Winsor I-like System, Langmuir, 1994, 10,2197-2201.
[82] Loh S.E., Gan L.M., Chew C. H. et al, Polemerization of methyl mathacrylate in winsor I-like system, J. Macromol. Sci., Pure ,Appl. Chem., 1996, A33, 371-384.
[83] 刘国军，王国昌，嵌段共聚物纳米结构材料，何天白，胡汉杰。海外高分子科学的新进展，1997年，第二版，39-50．
[84] Kortan A.R., Hull R., Opila R.L.. et al., Nucleation and Growth CdSe on ZnS Quantum Crystallite Seeds, and Vice verse, in Inverse Micelle Media. J. Am. Chem. Soc.. 1990,112.1317-1322.
[85] 李文华，王洪鉴，刘明翠等，W／O微孔液中Au／Fe_2O_3超微粒的制备，山东师大学报，1997，12(4)。406-410．
[86] Ogawa S., Kai Hu, Fu-Ren F. Fan, et al., Photoelectrochemistry of films of quantum size lead sulfide particles incorporated in self-assembled monolayers on gold, J. Phys Chem. B, 1997, 101, 5707-5711.
[87] Zou B.S., Little R.B., Wang J.P., et al., Effect of different capping environments on the optical Properties of CdS nanoparticles in reverse micelles, J. Inter. Quant. Chem., 1999, 75,439-450.
[88] Andrey J. Zarur and Jackie Y. Ying, Reverse microemulsion synthesis of nanostructured cornplex oxide for catalytic combustion, Nature, 2000, 403, 65-67.
[89] Shi-Jian Su, Noriyuki Kuramoto, Processable polyaniline-titanium dioxide nanocomposites: effect of titanium dioxide on the conductivity, Synth. Met., 2000,114,147-153.
[90] Alan G.Macdiarmid, Arthur Epstein, Secondary doping in polyaniline, Synth. Met.,1995,69,85-92.
[91] 刘成站，东北师范大学硕士学位论文，2001．
[92] Tzou K., Gregory R. V., Kinetic Study of the Chemical Polymerization of Aniline in Aqueous Solutions, Synth. Met, 1992,47,267.
[93] P.J.Kinlen, D.C.Silverman, C.R.Jeffreys, Corrosion protection using polyaniline coating formulations, Synth. Met, 1997,84-86, 1327.
[94] Li J. Kham T.M., Highly conductive solid polymer electrolytes prepared by blending high molecular weight poly (ethylene oxide), poly (2- or 4-vinylpyridine), and lithium perchlorate, Macromolecules, 1993, 26(17), 4544.
[95] 孟繁涛，东北师范大学硕士学位论文，1999．
[96] 刘景林，东北师范大学硕士学位论文，1997．
[97] 闫云，东北师范大学硕士学位论文，2000．
[98] Hailin Fan, Ying Chu, et al., Lipase-catalyzed synthesis of monoglcerides by hydrolysis of Sogban oil in AOT/iso-octane reversed micelles, Annals of the New York academy of sciences enzyme engineering. XIV, December 13,1998,267-272.
[99] 张薇，东北师范大学硕士学位论文，1998．
[100] 刘景林，史月华，褚莹等，AEOT／异新烷／水反胶束体系对血红蛋白的提取，高等学校化学学报，1999，120，1122-1124．
[101] 褚莹，孟繁涛，吴子尘等，反胶团法提取细胞色素C，东北师大学报，1994，2，133．
[102] 褚莹，纪建业，马占芳等，反胶团相转移法提纯酵母脂肪酶，高等学校化学学报，1997，10，1695-1697．
[103] 冯琳，东北师范大学硕士学位论文，2000。
[104] 陈悦，东北师范大学硕士学位论文，2001．
[105] Jinsong Tang, Xiabin Jing, Baochen Wang and Fosong Wang, Infrared spectra of soluble polyaniline, Synth. Met., 1988, 24,231-238.