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研究生:吳佳璇
研究生(外文):Chia-HsuanWu
論文名稱:超分子結構奈米銀膠體的製備與特性探討
論文名稱(外文):Fabrication and Characterization of Silver Nanoparticles Embedded in Supramolecular Organogels
指導教授:劉瑞祥
指導教授(外文):Jui-Hsiang Liu
學位類別:碩士
校院名稱:國立成功大學
系所名稱:化學工程學系碩博士班
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2012
畢業學年度:100
語文別:中文
論文頁數:89
中文關鍵詞:自組裝超分子凝膠氫鍵模板奈米銀粒子液晶
外文關鍵詞:self-assemblysupramolecular gelshydrogen bondmatricessilver nanoparticlesliquid crystals
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近年來,小分子凝膠被廣泛作為基質,透過凝膠與無機物的二次作用力,合成出各種不同結構的複合材料,如螺旋、纖維和絲狀等。此種新穎的有機-無機材料,深受化學界重視。為了合成出此種新穎的複合材料,我們研究合成出光學活性凝膠體分子(cholesteryl-pyridine-carbamate, CPC),將其分子設計上導入pyridine基團、膽固醇基團與胺酯基,藉由分子間的二次力鍵結,誘導CPC分子在有機溶劑中形成超分子凝膠體。由SEM與TEM結果顯示,此CPC分子可自組裝成奈米纖維進而組織成三維網絡的超分子凝膠(supramolecular gel);透過XRD與分子模擬程式分析,說明超分子有機凝膠以pyridine基團及胺酯基為重疊作錯位排列。並利用FTIR與變溫1H-NMR証實分子間氫鍵和凡德瓦力為凝膠形成的主要作用力。透過凝膠化測驗可得知最小臨界凝膠濃度。進一步的以超分子凝膠為基質(matrix),利用分子上的孤對電子對與銀離子產生螯合作用,以光化學反應還原吸附在凝膠纖維上的奈米銀粒子,使形成三維網絡的奈米銀膠。其次,凝膠分子上的pyridine 基團能與sebacic acid 形成氫鍵錯合物,經DSC、POM證實其具有熱變性液晶性質。

關鍵字:自組裝、超分子凝膠、氫鍵、模板、奈米銀粒子、液晶。

Low-molecular-weight-gelators (LMWGs) have recently been used as a matrix to construct a kind of composite materials of different shapes or structures such as helices, fibers, tapes or tubes through the secondary force interaction between gelators and inorganic materials. In order to develop this kind of novel composite materials, we synthesized and characterized the novel chiral molecule cholesteryl-pyridine-carmbamate (CPC) containing pyridine, cholesteryl and urethane group. Supramolecular organogels formed due to the secondary forces between CPC molecules and solvents. From the results of SEM and TEM analysis, self-assembly of CPC molecules form highly ordered nanofibers. Further aggregation of the ordered constructions forms 3D entangled network. XRD and molecular simulation show that arrangement of supramolecular organogel is mainly through the overlap of pyridine and urethane groups. Results of FTIR and thermal changeable 1H-NMR show that intermolecular hydrogen bond and van der Waals forces are the key factors for the formation of gels in DMSO. Furthermore, supramolecular gels were used as polymer matrices to coordinate silver ions. Silver nanoparticles embedded self-assembled nanofibers were further fabricated via photoreduction of silver ions. CPC forms complex with sebacic acid through hydrogen bond between pyridine and carboxylic group. Thermotropic liquid crystal phases of the complex were confirmed using DSC and POM analysis.
Keywords:self-assembly, supramolecular gels, hydrogen bond, matrices,silver nanoparticles, liquid crystals.

摘要………………………I
Abstract…………………………II
致謝……………………III
目錄……………………IV
示意圖……………… VII
圖目錄…………………IX
表目錄…………………XIV


第一章 緒論................1
1-1 前言...........................1
1-2 研究動機與方向 .........................2
第二章 文獻回顧................4
2-1 超分子化學..............4
2-2 自組裝超分子...............6
2-3 凝膠簡介.................8
2-3-1 依據介質類型分類.................9
2-3-2 依據組成和相互作用力分類...................10
2-4 超分子凝膠....................12
2-5 小分子有機凝膠體......................13
2-5-1 含膽固醇基凝膠...................14
2-5-1-1 ALS小分子凝膠.................15
2-5-1-2 A(LS)2 小分子凝膠..................22
2-5-2 超分子奈米線為基質合成無機奈米結構................26
2-5-3 感應和自發性凝膠...............29
2-5-4 凝膠-奈米粒子複合材料................32
2-5-5 雙成分系統..................35
第三章 實驗步驟.................36
3-1實驗藥品...................36
3-2實驗儀器..........................38
3-3 有機凝膠體的合成步驟.......................39
3-4 不同溶劑下自組裝形成凝膠能力之測試......................40
3-5 TEM、SEM、AFM和XRD試片製作...................41
3-5-1 TEM試片製作................41
3-5-2 SEM試片製作................41
3-5-3 AFM 試片製作...........41
3-5-4 XRD試片製作................41
3-6 變溫1H-NMR樣品製作 ................42
3-7 光還原奈米銀粒子...............42
3-7-1 金屬銀離子與CPC分子形成錯合物之1H-NMR樣品製作...........42
3-7-2 光化學還原奈米銀粒子................42
3-8 導入SEBACIC ACID與 CPC形成氫鍵錯合物.................43
第四章 結果與討論........................44
4-1 含pyridine基團的小分子凝膠(LMWGS)之鑑定...............44
4-2 含pyridine基團的小分子凝膠(LMWGS)自組裝行為探討.......46
4-2-1 CPC凝膠體於不同溶劑下凝膠化能力與臨界凝膠濃度之探討.......48
4-2-2 含pyridine凝膠體的排列堆疊機制研究探討..................53
4-2-3 CPC於溶劑DMSO凝膠的變溫1H-NMR核磁共振光譜探討..........56
4-2-4 自組裝超分子凝膠微結構之探討...............60
4-3 光化學法還原奈米銀粒子探討..................66
4-4 氫鍵錯合物探討.............77
第五章 結論..................84
參考文獻............................85


[1] J. M. Lehn, “upramolecular Chemistry-Scope and Perspectives Molecules-Supermolecules-Molecular Devices, Nobel Lecture, 27, 89 (1987).
[2] 楊吉水, “超分子化學, Chemistry, The Chinese Chemistry Society, Taipei, 62, 11 (2004).
[3] 邱泰翔,“環糊精-單體包容錯合物自組裝集合體及所形成螺旋高分子之製備及特性探討,國立成功大學化學工程研究所碩士論文, (2008)。
[4] 陳玟婷,“光學活性有機凝膠體之超分子自組裝與特性探討,國立成功大學化學工程研究所碩士論文 (2011)。
[5] G. M. Whitesides, “Beyond Molecules: Self-assembly of Mesoscopic and Macroscopic Components, Proc. Natl. Acad. Sci., 99, 4769 (2002).
[6] G. M. Whitesides, and B. Grzybowski, “Self-Assembly at All Scales, Science, 295, 2418 (2002).
[7] K. E. Schwiebert, J. C. MacDonald, and G. M. Whitesides, “Engineering the Solid State with 2-Benzimidazolones, J. Am. Chem. Soc., 118, 4018 (1996).
[8] L. S. Mende, R. H. Friend, and J. D. MacKenzie, “Self-Organized Discotic Liquid Crystals for High-Efficiency Organic Photovoltaics, Science, 293, 1119 (2001).
[9] E. L. Thomas, “The ABCs of Self-Assembly, Science, 286, 1307 (1999).
[10] S. Forster, “From Self-Organizing Polymers to Nanohybrid and Biomaterials, Angew. Chem., Int. Ed., 41, 688 (2002).
[11] D. Chapman, “Micelles, Monolayers and Biomembranes, Wiley Liss, New York, p479 (1995).
[12] G. M. Whitesides, “Patterned Self-Assembled Monolayers and Meso-Scale Phenomena, Acc. Chem. Res., 28, 219 (1995).
[13] V. Grantcharova, D. Baker, and A. L. Horwich, “Mechanisms of Protein Folding, Curr. Opin. Struct. Biol., 11, 70 (2001).
[14] H. Nabika, B. Takimoto, and K. Murakoshi, “Molecular Separation in The Lipid Bilayer Medium: Electrophoretic and Self-spreading Approaches, Anal. Bioanal. Chem., 391, 2497 (2008).
[15] N. M. Sangeetha, and U. Maitra, “Supramolecular Gels: Functions and Uses, Chem. Soc. Rev., 34, 821 (2005).
[16] 黃明華、牟中原,科學月刊雜誌社.金台灣資訊事業有限公司。
04, 160 (1983) .
[17] 李俊賢,“含N, N'-二苯吡啶醯胺凝膠分子其自組裝行為硏究,國立臺灣師範大學化學研究所碩士論文 (2009)。
[18] J. C. Leroux, “Organogels, and Their Use in Drug Delivery-A review, J. Controlled Release, 125, 179 (2008).
[19] 呂政錡,“含Urea基團Triazine與Triarylamine衍生物之新型凝膠分子於不同溶劑下凝集效應與光學性質影響之探討,國立臺灣科技大學高分子工程研究所博士論文 (2008)。
[20] S. Banerjee , R. K. Das, and U. Maitra, “Supramolecular Gels ‘In Action’ , J. Mater. Chem., 19, 6649 (2009).
[21] M. Zinic, F. Vogtle, and F. Fages, “Cholesterol-Based Gelators, Top. Curr. Chem., 256, 39 (2005).
[22] K. Murata, M. aoki, T. Suzuki, T. Harada, H. Kawabata, T. Komorti, F. Ohseto, K. Ueda, and S. Shinkai, “Thermal and Light Control of the Sol-Gel Phase Transition in Cholesterol-Based Organic Gels. Novel Helical Aggregation Modes As Detected by Circular Dichroism and Electron Microscopic Observation, J. Am. Chem. Soc., 116, 6664 (1994).
[23] K. J. C. van Bommel, A. Friggeri, and S. Shinkai, Arianna Friggeri, and Seiji Shinkai, “Organic Templates for the Generation of Inorganic Materials, Angew. Chem., Int. Ed., 42, 980 (2003).
[24] Q. T. Liu, Y. L. Wang, W. Li, and Wu, LX, “Structural Characterization and Chemical Response of a Ag-Coordinated Supramolecular Gel, Langmuir, 23, 8217 (2007).
[25] K. Sugiyasu, N. Fujita, M. Takeuchi, S. Yamada, and S. Shinkai, “Proton-sensitive Fuorescent Organogels, Org. Biomol. Chem., 1, 895 (2003).
[26] J. M. Lehn, M. Mascal, and J. Fischer, “Molecular Recognition directed Self-assembly of Ordered Supramolecular Strands by Cocrystallization of Complementary Molecular Components, Chem. Commun., 479 (1990).
[27] Y. P. Wu, S. Wu, X. J. Tian, X. Wang, W. X. Wu, G. Zou, and Q. J. Zhang, “Photoinduced Reversible Gel–sol Transitions of Dicholesterol-linked Azobenzene Derivatives through Breaking and Reforming of Van Der Waals Interactions, Soft Matter, 7, 167 (2011).
[28] M. Kimura, S. Kobayashi, T. Kuroda, K. Hanabusa, and H. Shirai, “Assembly of Gold Nanoparticles into Fibrous Aggregates Using Thiol-Terminated Gelators, Adv. Mater., 4, 16 (2004).
[29] M. Kimura, S. Kobayashi, T. Kuroda, K. Hanabusa, and H. Shirai , “Self-Assembled Helical Nanofibers Made of Achiral Molecular Disks Having Molecular Adapter, Chem. Mater., 22, 5732 (2010).
[30] M. Constantinos and D. Tsiourvas, “Thermotropic Liquid Crystals Formed by Intermolecular Hydrogen Bonding Interactions, Angew. Chem., Int. Ed., 34 , 1696 (1995).
[31] H. Hiroshl, Y. Yoshlro, Y. Akio, and K. Atsuhiro, “Photoreduction of Silver Ion in Aqueous and Alcoholic Solutions, J. Phys. Chem., 80, 25 (1976).
[32] J. Guo, F. Chen, Z. Qu, H. Yang, and J. Wei , Electrothermal Switching “Characteristics from a Hydrogen-Bonded Polymer Network Structure in Cholesteric Liquid Crystals with a Double-Handed Circularly Polarized Light Reflection Band, J. Phys. Chem. B, 115, 861 (2011).
[33] M. Llusar and C. Sanchez, “Inorganic and Hybrid Nanofibrous Materials Templated with Organogelators, Chem. Mater., 20, 782 (2008).
[34] J. H. Jung, M. Park, and S. Shinkai, “Fabrication of Silica Nanotubes by Using Self-assembled Gels and Their Applications in Environmental and Biological Felds, Chem. Soc. Rev., 39, 4286 (2010).
[35] B. Escuder, F. Rodrı´guez-Llansola, and J. F. Miravet, “Supramolecular Gels as Active Media for Organic Reactions and Catalysis, New J. Chem., 34, 1044 (2010).
[36] J. Liu, J. Yan, X. Yuan, K. Liu, J. Peng, and Y. Fang, “A novel low-molecular-mass gelator with a redox active ferrocenyl group:Tuning Gel Formation by Oxidation, J. Colloid Interface Sci., 318, 397 (2008).
[37] A. Kishimura, T. Yamashita, and T. Aida, “Phosphorescent Organogels via “Metallophilic Interactions for Reversible RGB-Color Switching, J. Am. Chem. Soc., 127, 179 (2005).

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