本研究為結合奈米自組裝(Self-assembly)技術與毛細管電泳技術製作開管式毛細管管柱進行毛細管電層析(Capillary Electrochromatography；CEC)分離中性分析物。本實驗使用化學還原法合成金奈米粒子，藉由金奈米粒子反覆自組裝烷基雙硫醇分子形成多層膜烷基靜相，且於最後一層金奈米粒子上鍵結長碳鏈烷基硫醇分子即完成開管式毛細管層析管柱。所合成之金奈米粒子以穿透式電子顯微鏡(Transmission Electron Microscopy；TEM) 鑑定其粒徑大小約13 nm且為球形分佈；且由掃瞄式電子顯微鏡(Scanning Electron Microscopy；SEM) 影像圖中可清楚看見金奈米粒子均勻地分佈在毛細管內壁表面。此研究以分析類固醇藥品(testosterone、progesterone及testosterone propionate)來探討自組裝毛細管管柱之性質，探討的參數包括：金奈米粒子自組裝層數、烷基硫醇分子及烷基雙硫醇分子的碳鏈長度、緩衝溶液中有機修飾劑含量、緩衝溶液之離子強度與pH值等。由實驗結果顯示，隨著自組裝層數越多分離效率越好，且以較長碳鏈之硫醇分子為靜相的分離效果較佳。實驗最後以管柱性質探討之最佳化條件應用於多環芳香烴化合物(Polycyclic Aromatic Hydrocarbons；PAHs)的分析，可成功地分離4種PAHs化合物naphthalene、fluorene、phenanthrene及pyrene。

The dissertation is to emphasize the feasibility of open-tubular capillary electrochromatography (OT-CEC), combining gold nanoparticle self assembly (SA) technique with capillary electrophoresis (CE). The capillary inner wall stationary phase was fabricated through layer-by-layer (LBL) of gold nanoparticles and alkanedithiol, and subsequent bonded alkanethiol on the end of gold nanoparticle. The size distribution of the spherical gold nanoparticles is about 13 nm, which is determined by transmission electron microscopy (TEM) photograph. Also the capillary of alkanethiol-modified gold nanoparticles was successfully characterized by scanning electron microscopy (SEM) image. The electrochromatographic behavior of the novel CEC column was obtained by separating three steroids (testosterone, progesterone and testosterone propionate) as model compounds, through variation of the number of gold nanoparticles layers, the chain length of the alkanedithiol and alkanethiol, the percentage of organic modifier, and the ionic strength and pH of running buffer. The results show that the separation efficiency is improved as gold nanoparticle layers increase, and a better resolution is obtained with longer alkyl chain of alkanedithiol and alkanethiol. Finally, the CEC system can successfully separate four PAHs (naphthalene, fluorine, phenanthrene and pyrene) under the optimum conditions.

Baker, D. R., "Capillary Electrophoresis", John Wiley: New York 1995,
Brust, M., Bethell, D., Kiely, C. J. and Schiffrin, D. J., "Self-Assembled Gold Nanoparticle Thin Films with Nonmetallic Optical and Electronic Properties", Langmuir 1998, 14, 5425-5429.
Cant, N. E., Critchley, K., Zhang, H.-L. and Evans, S. D., "Surface Functionalisation for the Self-Assembly of Nanoparticle/Polymer Multilayer Films", Thin Solid Films 2003a, 426, 31-39.
Cant, N. E., Zhang, H.-L., Critchley, K., Mykhalyk, T. A., Davies, G. R. and Evans, S. D., "Fabrication and Characterization of Self-Assembled Nanoparticle/Polyelectrolyte Multilayer Films", J. Phys. Chem. B 2003b, 107, 13557-13562.
Cheng, W., Dong, S. and Wang, E., "Site-Selective Self-assembly of MPA-Bridged CuHCF Multilayers on APTMS-Supported Gold Colloid Electrodes", Chem. Mater. 2003, 15, 2495-2501.
Cikalo, M. G., Bartle, K. D. and Myers, P., "Influence of the Electrical Double-Layer on Electroosmotic Flow in Capillary Electrochromatography", J. Chromatogr. A 1999, 836, 35-51.
Crego, A. L., Martínez, J. and Marina, M. L., "Influence of Mobile Phase Composition on Electroosmotic Flow Velocity, Solute Retention and Column Efficiency in Open-Tubular Reversed-Phase Capillary Electrochromatography", J. Chromatogr. A 2000, 869, 329-337.
Doron, A., Katz, E. and Willner, I., "Organization of Au Colloids as Monolayer Films onto IT0 Glass Surfaces: Application of the Metal Colloid Films as Base Interfaces To Construct Redox-Active Monolayers", Langmuir 1995, 11, 1313-1317.
Dun, H., Zhang, W., Wei, Y., Xiuqing, S., Li, Y. and Chen, L., "Layer-by-Layer Self-Assembly of Multilayer Zirconia Nanoparticles on Silica Spheres for HPLC Packings", Anal. Chem. 2004, 76, 5016-5023.
Elghanian, R., Storhoff, J. J., Mucic, R. C., Letsinger, R. L. and Mirkin, C. A., "Selective Colorimetric Detection of Polynucleotides Based on the Distance-Dependent Optical Properties of Gold Nanoparticles", Science 1997, 277, 1078-1080.
Finayson-Pitts, B. J., Pitts, J. N. and Jr., "Atmospheric Chemistry: Fundamentals and Experimental Techniques", JOHN WILEY and SONS, New York 1986,
Frens, G., "Controlled Nucleation for the Regulation of the Particles Size in Monodisperse Gold Suspensions", Nature Physical Science 1973, 241, 20-22.
Fujimoto, C. and Muranaka, Y., "Electrokinetic Chromatography Using Nanometer-Sized Silica Particles as the Dynamic Stationary Phase", J. High. Resol. Chromatogr. 1997, 20, 400-402.
Grabar, K. C., Freeman, R. G., Hommer, M. B. and Natan, M. J., "Preparation and Characterizationof Au Colloid Monolayers", Anal. Chem. 1995, 67, 735-743.
Gross, G. M., Nelson, D. A., Grate, J. W. and Synovec, R. E., "Monolayer-Protected Gold Nanoparticles as a Stationary Phase for Open Tubular Gas Chromatography", Anal. Chem. 2003, 75, 4558-4564.
Guihen, E. and Glennon., J. D., "Recent Highlights in Stationary Phase Design for Open-Tubular Capillary Electrochromatography", J. Chromatogr. A 2004, 1044, 67-81.
Holder, S. J., Elemans, J. A. A. W., Donners, J. J. J. M., Boerakker, M. J., Gelder, R. d., Barberá, J., Rowan, A. E. and Nolte, R. J. M., "Lamellar Organic Thin Films through Self-Assembly and Molecular Recognition", J. Org. Chem. 2001, 66, 391-399.
Jia, J., Wang, B., Wu, A., Cheng, G., Li, Z. and Dong, S., "A Method to Construct a Third-Generation Horseradish Peroxidase Biosensor: Self-Assembling Gold Nanoparticles to Three-Dimensional Sol-Gel Network", Anal. Chem. 2002, 74, 2217-2223.
Jinno, K. and Sawada, H., "Recent Trends in Open-Tubular Capillary Electrochromatography", Trends Anal. Chem. 2000, 19, 664-674.
Kapnissi-Christodoulou, C. P., Zhu, X. and Warner, I. M., "Analytical Separations in Open-Tubular Capillary Electrochromatography", Electrophoresis 2003, 24, 3917-3934.
Kirkland, J. J., "Stability of Silica-Based, Monofunctional C18 Bonded-Phase Column Packing for HPLC at High pH", J. Chromatogr. Sci. 1996, 34, 309-313.
Kleindienst, G., Huber, C. G., Gjerde, D. T., Yengoyan, L. and Bonn, G. K., "Capillary Electrophoresis of Petides and Proteins in Fused-Silica Capillaries Coated with Derivatized Polystyrene Nanoparticles", Electrophoresis 1998, 19, 262-29.
Kölbel, M. and Menger, F. M., "Molecular Recognition among Structurally Similar Components of a Self-Assembling Soft Material", Langmuir 2001, 17, 4490-4492.
Lee, T. M.-H., Li, L.-L. and Hsing, I.-M., "Enhanced Electrochemical Detection of DNA Hybridization Based on Electrode-Surface Modification", Langmuir 2003, 19, 4338-4343.
Li, W., Huo, L., Wang, D., Zeng, G., Xi, S., Zhao, B., Zhu, J., Wang, J., Shen, Y. and Lu, Z., "Self-Assembled Multilayers of Alternating Gold Nanoparticles and Dithiols: Approaching to Superlattice", Colloids and Surfaces A: Physicochemical and Engineering Aspects 2000, 175, 217-233.
Lin, Y.-W., Huang, M.-J. and Chang, H.-T., "Analysis of Double-Stranded DNA by Microchip Capillary Electrophoresis using Polymer Solutions Containing Gold Nanoparticles", J. Chromatogr. A 2003, 1014, 47-55.
Link, S. and El-Sayed, M. A., "Size and Temperature Dependence of the Plasmon Absorption of Colloidal Gold Nanoparticles", J. Phys. Chem. B 1999, 103, 4212-4217.
Liu, F.-K., Wei, G.-T. and Cheng, F.-C., "Immobilization of a Monolayer of Bovine Serum Albumin on Gold Nanoparticles for Stereo-specified Recognition of Dansyl-norvaline", J. Chin. Chem. Soc. 2003, 50, 931-937.
Maloney, T. D. and Colón, L. A., "A Drying Step in the Protocol to Pack Capillary Column by Centripetal Force for Capillary Electrochromatography", Electrophoresis 1999, 20, 2360-2365.
Menzie, C. A. and Potocki, B. B., "Exposure to Carcinogenic PAHs in the Environment", Environ. Sci. Technol. 1992, 26, 1278-1284.
Mirkin, C. A., "Programming the Assembly of Two- and Three Dimensional Architectures with DNA and Nanoscale Inorganic Building Blocks", Inorg. Chem. 2000, 39, 2258-2272.
Miura, Y., Sato, H., Ikeda, T., Sugimura, H., Takai, O. and Kobayashi, K., "Micropatterned Carbohydrate Displays by Self-Assembly of Glycoconjugate Polymers on Hydrophobic Templates on Silicon", Biomacromolecules 2004, 5, 1708-1713.
Murrihy, J. P., Breadmore, M. C., Tan, A., McEnery, M., Alderman, J., O’Mathuna, C., O’Neill, A. P., O’Brien, P., Advoldvic, N., Haddad, P. R. and Glennon, J. D., "Ion Chromatography on-Chip", J. Chromatogr. A 2001, 924, 233-238.
Neiman, B., Grushka, E. and Lev, O., "Use of Gold Nanoparticles To Enhance Capillary Electrophoresis", Anal. Chem. 2001, 73, 5220-5227.
Nuzzo, R. G. and Allara, D. L., "Adsorption of Bifunctional Organic Disulfides on Gold Surfaces", J. Am. Chem. Soc. 1983, 105, 4481-4483.
O'Mahony, T., Owens, V. P., Murrihy, J. P., Guihen, E., Holmes, J. D. and Glennon, J. D., "Alkylthiol Gold Nanoparticles in Open-Tubular Capillary Electrochromatography", J. Chromatogr. A 2003, 1004, 181-193.
Peng, Z., Walther, T. and Kleinermanns, K., "Influence of Intense Pulsed Laser Irradiation on Optical and Morphological Properties of Gold Nanoparticle Aggregates Produced by Surface Acid-Base Reactions ", Langmuir 2005, 21, 4249-4253.
Pretorius, V., Hopkins, B. J. and Schieke, J. D., "A New Concept For High-speed Liquid Chromatography", J. Chromatogr. A 1974, 99, 23-30.
Pumera, M., Wang, J., Grushka, E. and Polsky, R., "Gold Nanoparticle-Enhanced Microchip Capillary Electrophoresis", Anal. Chem. 2001, 73, 5625-5628.
Qian, L., Gao, Q., Song, Y., Li, Z. and Yang, X., "Layer-by-Layer Assembled Multilayer Films of Redox Polymers for Electrocatalytic Oxidation of Ascorbic Acid", Sens. Actuators. B Chem 2004, 27, 303-310.
Qu, X., Peng, Z., Jiang, X. and Dong, S., "Surface Charge Influence on the Surface Plasmon Absorbance of Electroactive Thiol-Protected Gold Nanoparticles ", Langmuir 2004, 20, 2519-2522.
Reynolds, K. J. and Colón, L. A., "Capillary Electrochromatography in Columns Packed by Gravity", Analyst 1998, 123, 1493-1495.
Robson, M. M., Cikalo, M. G., Myers, P., Euerby, M. R. and Bartle, K. D., "Capillary Electrochromatography: A Review", J. Microcol. Sep. 1997, 9, 357-372.
Robson, M. M., Roulin, S., Shariff, S. M., Raynor, M. W., Bartle, K. D., Clifford, A. A., Myers, P., Euerby, M. R. and Johnson, C. M., "Capillary Electrochromatography Using Columns Packed with a Supercritical Fluid Carrier", Chromatographia 1996, 43, 313-321.
Russo, M. V. and Goretti, G., "Hydrophobic-Phase-Modified Fused-Silica Columns for Capillary Electrophoresis", J. Chromatogr. A 2000, 871, 279-287.
Sato, T., Ahmed, H., Brown, D. and Johnson, B. F. G., "Single Electron Transistor Using a Molecularly Linked Gold Colloidal Particle Chain", J. Appl. Phys. 1997, 82, 696-701.
Schmid, G., "Nanoparticles: From Theory to Application", 2004,
Schwer, C. and Kenndler, E., "Electrophoresis in Fused-Silica Capillaries: The Influence of Organic Solvents on the Electroosmotic Velocity and the Zeta Potential", Anal. Chem. 1991, 63, 1801-1807.
Seitz, O., Chehimi, M. M., Cabet-Deliry, E., Truong, S., Felidj, N., Perruchot, C., Greaves, S. J. and Watts, J. F., "Preparation and Characterisation of Gold Nanoparticle Assemblies on Silanised Glass Plates", Colloids and Surfaces A: Physicochem. Eng. Aspects 2003, 218, 225-239.
Shimada, K., Mitamura, K. and Higashi, T., "Review: Gas Chromatography and High-Performance Liquid Chromatography of Natural Steroids", J. Chromatogr. A 2001, 935, 141-172.
Smith, R. K., Lewis, P. A. and Weiss, P. S., "Review: Patterning Self-Assembled Monolayers", Prog. Surf. Sci. 2004, 75, 1-68.
Stamou, D., Musil, C., Ulrich, W.-P., Leufgen, K., Padeste, C., David, C., Gobrecht, J., Duschl, C. and Vogel, H., "Site-Directed Molecular Assembly on Templates Structured with Electron-Beam Lithography", Langmuir 2004, 20, 3495-3497.
Tang, Q. and Lee, M. L., "Column Technology for Capillary Electrochromatography", Trends Anal. Chem. 2000, 19, 648-663.
Tanii, T., Hosaka, T., Miyake, T., Zhang, G.-J., Zako, T., Funatsu, T. and Ohdomari, I., "Preferential Immobilization of Biomolecules on Silicon Microstructure Array by means of Electron Beam Lithography on Organosilane Self-Assembled Monolayer Resist", Appl. Surf. Sci. 2004, 234, 102-106.
Thompson, D. W. and Collins, I. R., "Electrical Properties of the Gold-Aqueous Solution Interface", J. Colloid Interface Sci. 1992, 152, 197-204.
Tsuda, T., Nomura, D. and Nakagawa, G., "Open-Tubular Microcapillary Liquid Chromatography With Electro-Osmosis Flow Using A UV Detector", J. Chromatogr. 1982, 248, 241-247.
Ulman, A., "Formation and Structure of Self-Assembled Monolayers", Chem. Rev. 1996, 96, 1533-1554.
Viberg, P., Jornten-Karlsson, M., Petersson, P., Spégel, P. and Nilsson, S., "Nanoparticles as Pseudostationary Phase in Capillary Electrochromatography/ESI-MS", Anal. Chem. 2002, 74, 4595-4601.
Yan, C., "Electrokinetic Packing of Capillary Columns", No. 5,453,163 U.S. Patent 1995,
Yang, L., Guihen, E. and Glennon, J. D., "Alkylthiol Gold Nanoparticles in Sol-Gel-Based Open Tubular Capillary Electrochromatography", J. Sep. Sci. 2005a, 28, 757-766.
Yang, L., Guihen, E., Holmes, J. D., Loughran, M., O'Sullivan, G. P. and Glennon, J. D., "Gold Nanoparticle-Modified Etched Capillaries for Open-Tubular Capillary Electrochromatography", Anal. Chem. 2005b, 77, 1840-1846.
林淵宗, "多環芳香烴化合物類（PAHs）對人體的影響", 行政院環保署雙月刊，第66期 2003.
馬振基, "奈米材料科技原理與應用", 2003.
馬遠榮, "奈米科技", 2002.
郭清癸, 黃俊傑 and 牟中原, "金屬奈米粒子的製造", 物理雙月刊第六期 2001, 6, 614-624.
陳俊顯, "以奈米微粒篩檢特定鹼基序列之DNA", 自然科學簡訊第二期 2001, 13, 55-57.
陳楚驤, 林松香 and 包盛盈, "自我組合與奈米科技", 工業材料雜誌第179期 2001, 96-99.
潘福, 李獅慶, 張固剛, 蕭明熙 and 尹士俊, "生物化學", 1993.
蔡信行 and 孫光中, "奈米科技導論", 2004.
薛家倩 and 董玉平, "生醫感測技術之表面修飾化學", 工業材料雜誌第201期 2003, 164-173.
羅吉宗, 戴明鳳, 鄭振宗, 蘇程裕 and 吳育民, "奈米科技導論", 2003.