本研究是以Triethylenetetramine為親水基主體，與1,2-Epoxydodecane反應形成一雙親分子，並探討其溶液性質與用以製備自組裝球型金奈米粒子，並進一步分析推測形成球型聚集體的原理與機制。首先以傅立葉轉換紅外線光譜儀(FT-IR)及核磁共振光譜儀(NMR)、元素分析儀(EA)、高解析氣相層析質譜儀(GC-Mass)與Total Amine Value的測定確認雙親分子結構及純度；接著經由界面張力(surface tension)、螢光強度(I1/I3 value)與濁度(turbidity)的測定，推測出雙親分子於水溶液中聚集體產生的臨界聚集濃度，並利用動態粒徑分析儀(DLS)、穿透式電子顯微鏡(TEM)與X光繞射儀(XRD) 確認其聚集體的大小與種類；最後以此雙親分子作為保護劑及還原劑，用以製備自組裝球型金奈米粒子，研究在各種不同反應條件與雙親分子構造的情形下，對製備球型聚集體的影響。
實驗結果顯示，此雙親分子於水溶液中聚集體產生的臨界聚集濃度約為0.01 g/L，且其聚集體的形態為具有雙層膜結構之液胞；以其製備金奈米粒子時，當反應條件為[N]/[Au3+] = 20且pH = 3.2時，為一最佳製備自組裝球型金奈米粒子的條件；若此種分子結構無親油基部份或是親水基部份較長，皆無法製備出球型聚集體，表示需有親油基且適當量之乙烯亞胺的結構，才可製備出自組裝球型金奈米粒子；此約為200 nm的球型聚集體，是由粒徑約為19 nm的金粒子聚集組成，並可藉由控制pH值改變其形態；此球型聚集體對於時間相當穩定，而對還原方式、溶劑與溫度則相當敏感；於製備金奈米粒子系統中加入膽固醇後，可有效增進自組裝的行為，並使得所生成的球型聚集體尺寸較大且較不均勻。

In this study, dodecyl chain was introduced into triethylenetetramine to produce a new type amphiphile by a simple reaction. This amphiphile was characterized by FT-IR, NMR, EA, GC-Mass, and potentiometric titration. The critical aggregate concentration (CAC) of amphiphile in dilute aqueous solution was observed to be at the concentration of 0.01 g/L by the measurements of surface tension, the fluorescence intensity ratio, and turbidity. Negative stained TEM morphologies and XRD characterization indicate that the self-assembled aggregates of amphiphile were in the form of bilayer membranes or vesicles in dilute aqueous solution. The amphiphile stabilized and reduced gold nanoparticles were characterized by UV-visible spectrophotometer, TEM, and SEM, and the effects of different conditions like pH value, concentrations of amphiphile or HAuCl4 on the formation of gold nanoparticles were also investigated. From the experimental results, it is the best condition to prepare uniform self-assembly spherical aggregates at pH = 3.2 when the concentration [N]/[Au3+] = 20. The reduced gold nanoparticles undergo pH-tunable aggregation to create the intriguing microstructures. The spherical aggregates are stable for months in dilute aqueous solution but sensitivity for reducing method, solvent, and temperature. When adding cholesterol into the above mentioned system, the self-assembled behave would be more efficient and produce larger non-uniform size spherical aggregates.

1.蘇品書，超微粒子材料技術，復漢出版社，台南市，1989年。
2.莊萬發，超微粒子理論應用，復漢出版社，台南市，1995年。
3.Gűnter Schmid, Clusters and Colloids: From Theory to Applications, VCH, New York, 1994.
4.Jin-Ho Choy, Jong-Seok Yoo, Yang-Su Han, Yoon-Ho Kim,Citrate sol-gel method for the preparation of β/β′'-alumina, Materials Letters, 16, 4, 226, 1993.
5.Janos H. Fendler, Atomic and molecular clusters in membrane mimetic chemistry, Chemical Reviews, 87, 5, 877, 1987.
6.Thomas Linnert, Paul Mulvaney, Arnim Henglein, Surface chemistry of colloidal silver: surface plasmon damping by chemisorbed iodide, hydrosulfide, and phenylthiolate, The Journal of Physical Chemistry, 93, 3, 679, 1993.
7.N. Ichinose, Y. Ozaki and S. Kashu, Superfine Particle Technology, Springer-Verlag, London, 1992.
8.葉伊同，特殊金屬奈米結構材料，中正大學化學研究所碩士論文，1998年。
9.Ser-Sing Chang, Chao-Wen Shih, Cheng-Dah Chen, Wei-Cheng Lai, C. R. Chris Wang, The Shape Transition of Gold Nanorods, Langmuir, 15, 3, 701, 1999.
10.Manfred T. Reetz, Wolfgang Helbig, Size-Selective Synthesis of Nanostructured Transition Metal Clusters, Journal of the American Chemical Society, 116, 16, 7401, 1994.
11.Manfred T. Reetz, Wolfgang Helbig, Stefan A. Quaiser, Electrochemical Preparation of Nanostructural Bimetallic Clusters, Chemistry of Materials, 7, 12, 2227, 1995.
12.Arnim Henglein, Physicochemical properties of small metal particles in solution: "microelectrode" reactions, chemisorption, composite metal particles, and the atom-to-metal transition, The Journal of Physical Chemistry, 97, 21, 5457, 1993.
13.C. de Cointet, M. Mostafavi, J. Khatouri, and J. Belloni, Growth and Reactivity of Silver Clusters in Cyanide Solution, Journal of Physical Chemistry B, 101, 18, 3512, 1997.
14.A. Henglein and R. Tausch-Treml, Optical absorption and catalytic activity of subcolloidal and colloidal silver in aqueous solution: A pulse radiolysis study, Journal of Colloid and Interface Science, 80, 1, 84, 1981.
15.Yoshiro Yonezawa, Tomoo Sato, Shigeru Kuroda and Ken-ichi Kuge, Photochemical formation of colloidal silver: peptizing action of acetone ketyl radical, Journal of the Chemical Society - Faraday Transactions, 87, 1905, 1991.
16.M. Y. Han and C. H. Quek, Photochemical Synthesis in Formamide and Room-Temperature Coulomb Staircase Behavior of Size-Controlled Gold Nanoparticles, Langmuir, 16, 362, 2000.
17.Kenji Okitsu, Hiroshi Bandow, and Yasuaki Maeda, Sonochemical Preparation of Ultrafine Palladium Particles, Chemistry of Materials, 8, 2, 315, 1996.
18.Link, S., Wang, Z. L., and El-Sayed, M. A, Alloy Formation of Gold-Silver Nanoparticles and the Dependence of the Plasmon Absorption on Their Composition, Journal of Physical Chemistry B, 103, 18, 3529, 1999.
19.John Turkevich, and Gwan Kim, Palladium: Preparation and Catalytic Properties of Particles of Uniform Size, Science, 169, 873, 1970.
20.Naoki Toshima, Masafumi Harada, Yoshinao Yamazaki, and Kiyotaka Asakura, Catalytic activity and structural analysis of polymer-protected gold-palladium bimetallic clusters prepared by the simultaneous reduction of hydrogen tetrachloroaurate and palladium dichloride, The Journal of Physical Chemistry, 96, 24, 9927, 1992.
21.Claudio Sangregorio, Monica Galeotti, Ugo Bardi, and Piero Baglioni, Synthesis of Cu3Au Nanocluster Alloy in Reverse Micelles, Langmuir, 12, 24, 5800, 1996.
22.Helmut Bönnemann, Ryan M. Richards, Nanoscopic Metal Particles - Synthetic Methods and Potential Applications, European Journal of Inorganic Chemistry, 2001, 10, 2455, 2001.
23.Michael Faraday, The Bakerian Lecture: Experimental Relations of Gold (and Other Metals) to Light, Philosophical Transactions of the Royal Society of London, 147, 145, 1857.
24.John Turkevich, Peter Cooper Stevenson, and James Hillier, A study of the nucleation and growth processes in the synthesis of colloidal gold, Discussions of the Faraday Society, 11, 55, 1951.
25.Ziyi Zhong, Alamelu Suriya Subramanian, James Highfield, Keith Carpenter, and Aharon Gedanken, From Discrete Particles to Spherical Aggregates: A Simple Approach to the Self-Assembly of Au Colloids, Chemistry A European Journal, 11, 1473, 2005.
26.Andrew K. Boal, Faysal Ilhan, Jason E. DeRouchey, Thomas Thurn-Albrecht, Thomas P. Russell, and Vincent M. Rotello, Self-assembly of nanoparticles into structured sphericaland network aggregates, Nature, 404, 13, 746, 2000.
27.Xiaohong Li, Yunchao Li, Yiwei Tan, Chunhe Yang, and Yongfang Li, Self-Assembly of Gold Nanoparticles Prepared with 3,4-Ethylenedioxythiophene as Reductant, Journal of Physical Chemistry B, 108, 17, 5192, 2004.
28.Andrew K. Boal, Mark Gray, Faysal Ilhan, Gilles M. Clavier, Laura Kapitzky and Vincent M. Rotello, Bricks and mortar self-assembly of nanoparticles, Tetrahedron, 58, 4, 765, 2002.
29.Andrew K. Boal, Benjamin L. Frankamp, Oktay Uzun, Mark T. Tuominen, and Vincent M. Rotello, Modulation of Spacing and Magnetic Properties of Iron Oxide Nanoparticles through Polymer-Mediated ”Bricks and Mortar” Self-assembly, Chemistry of Materials, 16, 3252, 2004.
30.Lomax, Eric G., Amphoteric surfactants, M. Dekker, New York, 1996.
31.M. R. Porter, Handbook of surfactants, Blackie, Glasgow, 1991.
32.Ijeoma F. Uchegbu, Synthetic surfactant vesicles：niosomes and other non-phospholipid vesicular systems, Harwood Academic, Australia, 2000.
33.Jorg Kreuter, Colloidal drug delivery systems, M. Dekker, New York, 1994.
34.R.R.C. New, Liposomes : a practical approach, IRL Press, Oxford, 1990.
35.Morton Rosoff, Vesicles, M. Dekker, New York, 1996.
36.Gregory Gregoriadis and Alexander T. Florence, Harish M. Patel, Liposomes in drug delivery, Harwood Academic, Switzerland, 1993.
37.Santanu Bhattacharya, and Saubhik Haldar, Interactions between cholesterol and lipids in bilayer membranes. Role of lipid headgroup and hydrocarbon chain-backbone linkage, Biochimica et Biophysica Acta, 1467, 39, 2000.
38.Fredric M. Menger, Ashley L. Galloway, and Mary E. Chlebowski, Surface Tension of Aqueous Amphiphiles, Langmuir, 21, 20, 9010, 2005.
39.Toyoki Kunitake, Yoshio Okahata, Masatsugu Shimomura, Sho-ichiro Yasunami, and Kunihide Takarabe, Formation of Stable Bilayer Assemblies in Water from Single-Chain Amphiphiles. Relationship between the Amphiphile Structure and the Aggregate Morphology, Journal of the American Chemical Society, 103, 5401, 1981.
40.Toyoko Imae, and Beth Trend, Video-Enhanced Differential Interference Contrast Microscope Observation of pH-Dependent Vesicle Formation by Single-Chain Surfactants, Langmuir, 7, 643, 1991.
41.Nobuo Kimizuka, Takayoshi Kawasaki, Kiyoko Hirata, and Toyoki Kunitake, Supramolecular Membranes. Spontaneous Assembly of Aqueous Bilayer Membrane via Formation of Hydrogen Bonded Pairs of Melamine and Cyanuric Acid Derivatives, Journal of the American Chemical Society, 120, 4094, 1998.
42.Wei Wang, Xiaozhong Qu, Alexander I. Gray, Laurence Tetley, and Ijeoma F. Uchegbu, Self-Assembly of Cetyl Linear Polyethylenimine To Give Micelles, Vesicles, and Dense Nanoparticles, Macromolecules, 37, 24, 9114, 2004.
43.Xianchun Lu, Zhiqiang Zhang, and Yingqiu Liang, Bilayer Formation in Dilute Aqueous Solution from Monoalkylethylenediamine, Langmuir, 12, 5501, 1996.
44.Xianchun Lu, Zhiqiang Zhang, and Yingqiu Liang, Complexed Bilayer Membranes with Novel Structural Features Formed by Single-Chain Amphiphiles, Langmuir, 13, 533, 1997.
45.Chun Li, Xianchun Lu, and Yingqiu Liang, Effect of Counterions on the Organized Structure of Cu2+-Coordinated Bilayer Membranes Formed by Monoalkyl Derivatives of Ethylenediamine, Langmuir, 18, 575, 2002.
46.Ping-Lin Kuo, Chi-Chang Chen, and Mei-Wen Jao, Effects of Polymer Micelles of Alkylated Polyethylenimines on Generation of Gold Nanoparticles, Journal of Physical Chemistry B, 109, 9445, 2005.
47.Adina Haimov, Hagai Cohen, and Ronny Neumann, Alkylated Polyethyleneimine/ Polyoxometalate Synzymes as Catalysts for the Oxidation of Hydrophobic Substrates in Water with Hydrogen Peroxide, Journal of the American Chemical Society, 126, 11762, 2004.
48.Dagmar Fischer, Anke von Harpe, Klaus Kunath, Holger Petersen, Youxin Li, and Thomas Kissel, Copolymers of Ethylene Imine and N-(2-Hydroxyethyl)-ethylene Imine as Tools To Study Effects of Polymer Structure on Physicochemical and Biological Properties of DNA Complexes, Bioconjugate Chemistry, 13, 1124, 2002.
49.B. D. Cullity, Elements of x-ray diffraction, Addison-Wesley, Canada, 1978.
50.Xuping Sun, Shaojun Dong, and Erkang Wang, One-step synthesis and characterization of polyelectrolyte-protected gold nanoparticles through a thermal process, Polymer, 45, 2181, 2004.
51.Sheng Tian Wang, Ji Cang Yan, and Li Chen, Formation of gold nanoparticles and self-assembly into dimer and trimer aggregates, Materials Letters, 59, 11, 1383, 2005.
52.Xuping Sun, Shaojun Dong, and Erkang Wang, Large-Scale Synthesis of Micrometer-Scale Single-Crystalline Au Plates of Nanometer Thickness by a Wet-Chemical Route, Angewandte Chemie International Edition, 43, 6360, 2004.
53.Luyan Wang, Xiao Chen, Jie Zhan, Zhenming Sui, Jikuan Zhao, and Zhenwen Sun, Controllable Morphology Formation of Gold Nano- and Micro-plates in Amphiphilic Block Copolymer-based Liquid Crystalline Phase, Chemistry Letters, 33, 6, 720, 2004.
54.Luyan Wang, Xiao Chen, Jie Zhan, Yongcun Chai, Chunjie Yang, Limei Xu, Wenchang Zhuang, and Bo Jing, Synthesis of Gold Nano- and Microplates in Hexagonal Liquid Crystals, Journal of Physical Chemistry B, 109, 3189, 2005.
55.Savka I. Stoeva, Vladimir Zaikovski, B. L. V. Prasad, Peter K. Stoimenov, Christopher M. Sorensen, and Kenneth J. Klabunde, Reversible Transformations of Gold Nanoparticle Morphology, Langmuir, 21, 23, 10280, 2005.
56.Xiaohong Li, Yunchao Li, Chunhe Yang, and Yongfang Li, Liposome Induced Self-Assembly of Gold Nanoparticles into Hollow Spheres, Langmuir, 20, 3734, 2004.
57.John Fink, Christopher J. Kiely, Donald Bethell, and David J. Schiffrin, Self-Organization of Nanosized Gold Particles, Chemistry of Materials, 10, 3, 922, 1998.
58.Daniel V. Leff, Lutz Brandt, and James R. Heath, Synthesis and Characterization of Hydrophobic, Organically-Soluble Gold Nanocrystals Functionalized with Primary Amines, Langmuir, 12, 4723, 1996.
59.Ashavani Kumar, Saikat Mandal, P.R. Selvakannan, Renu Pasricha, A. B. Mandale, and Murali Sastry, Investigation into the Interaction between Surface-Bound Alkylamines and Gold Nanoparticles, Langmuir, 19, 6277, 2003.
60.Lixue Zhang, Xuping Sun, Yonghai Song, Xiue Jiang, Shaojun Dong, and Erkang Wang, Didodecyldimethylammonium Bromide Lipid Bilayer-Protected Gold Nanoparticles: Synthesis, Characterization, and Self-Assembly, Langmuir, 22, 6, 2838, 2006.
61.Han-Pu Liang, Li-Jun Wan, Chun-Li Bai, and Li Jiang, Gold Hollow Nanospheres: Tunable Surface Plasmon Resonance Controlled by Interior-Cavity Sizes, Journal of Physical Chemistry B, 109, 7795, 2005.
62.Savka I. Stoeva, B. L. V. Prasad, Sitharaman Uma, Peter K. Stoimenov, Vladimir Zaikovski, Christopher M. Sorensen, and Kenneth J. Klabunde, Face-Centered Cubic and Hexagonal Closed-Packed Nanocrystal Superlattices of Gold Nanoparticles Prepared by Different Methods, Journal of Physical Chemistry B, 107, 7441, 2003.
63.Gareth Thomas, Transmission electron microscopy of metals, Wiley, New York, 1962.
64.Nicholas J. Turro, Bruce H. Baretz, Ping Lin Kuo, Photoluminescence probes for the investigation of interactions between sodium dodecylsulfate and water-soluble polymers, Macromolecules, 17, 1321, 1984.
65.K. P. Ananthapadmanabhan, E. D. Goddard, N. J. Turro, and P. L. Kuo, Fluorescence probes for critical micelle concentration determination, Langmuir, 1, 352, 1985.
66.徐銓亨，親油基化聚乙烯亞胺之合成與其在製備金屬奈米粒子及燃料電池觸媒之應用，成功大學化學工程研究所碩士論文，2006年。
67.陳啟漳，有機胺對製備金屬奈米粒子效應之研究，成功大學化學工程研究所博士論文，2005年。