高分子與兩性界面活性劑(amphiphilic surfactant)錯合所形成的長程有序奈米結構為錯合物中極性(高分子主鏈以及界面活性劑頭基)和非極性(界面面活性劑烷鏈)之間的微相分離所致。在這項研究中，我們驗證了界面活性劑十二烷基硫酸鈉（Sodium dodecyl sulfate, SDS）與所有胺基均帶正電的第四代聚乙二胺樹枝狀高分子(poly(amidoamine) (PAMAM) G4 dendrimer) 的靜電錯合擾動了由SDS所形成的圓柱形微胞。此擾動使微胞排列成面非六邊形的晶格。面心矩形柱狀(centered-rectangular columnar phase)並具有cmm非六邊形的晶格對稱性，此為一帶狀相(ribbon phase)。在SDS與PAMAM G4 dendrimer胺基團的莫耳比範圍內，SDS所形成的微胞排列成面心矩形柱狀(centered-rectangular columnar phase)並具有cmm非六邊形的晶格對稱性。若在界面活性劑SDS與PAMAM G4 dendrimer胺基團的莫耳比相同的情況下錯合，則SDS所形成的微胞排列成單斜柱狀(oblique columnar) 並具有p2斜晶格的對稱性，此兩種柱狀結構均屬於帶狀相結構(ribbon phase)。經過詳細分析容納在由SDS所形成的微胞圓柱體間隙中的PAMAM G4 dendrimer其幾何形狀後，得知PAMAM G4 dendrimer沿著SDS柱狀微胞的長軸被拉長形變為長橢球形，藉此增強兩帶電分子之間的電荷匹配。PAMAM G4 dendrimer的形變程度由靜電自由能(electrostatic free energy)和與變形相關的彈性自由能(elastic free energy)之間的相互作用決定。此外，本研究亦發現在加入鹽類的情況下進行錯合得以緩解PAMAM G4 dendrimer的形變。
除帶狀相結構外，透過調節PAMAM G4 dendrimer的質子化度（dp）和SDS與PAMAM G4 dendrimer的結合率（X），由SAXS結果可得知具有不同dp/X的錯合物可形成體心立方相（Body-centered cubic, BCC）、向列液晶相（Ncol）和其他四種類型的二維柱狀液晶相(2D columnar mesophase)。這些二維柱狀液晶相由PAMAM G4 dendrimer容納在SDS柱狀微胞的間隙所組成，包括六角柱狀相（Colhex），簡單矩形柱狀相（Colsr），單斜柱狀相（Colob）和面心矩形柱狀相（Colcr）。對錯合物中PAMAM G4 dendrimer的幾何結構進行詳細分析可得知，結構的轉變是由PAMAM G4 dendrimer的橫向和軸向變形與SDS微胞的橫截面變形之間的相互作用控制的，兩作用均為提升帶正電的PAMAM G4 dendrimer語帶負電的SDS微胞之間的電荷匹配。本研究證明了PAMAM G4 dendrimer通過靜電相互作用可誘發界面活性劑所形成的圓柱形微胞堆積成豐富的柱狀中間相，此為其開發功能材料的潛力。

The complexation of polymer with amphiphilic surfactant offers a facile route for constructing long-range ordered nanostructures via microphase separation between polar and nonpolar components in the complex. In this study, we demonstrate that the electrostatic complexation of anionic sodium dodecyl sulfate (SDS) surfactant with a positively charged colloid-like macromolecule, poly(amidoamine) (PAMAM) G4 dendrimer perturbed the packing habit of SDS cylindrical micelles to non-hexagonal two-dimensional lattice, forming the ribbon phase. The cylindrical micelles organized in the centered rectangular lattice with orthorhombic cmm symmetry over a broad range of surfactant-to-dendrimer amine group molar ratio. The packing mode transformed to the oblique lattice with monoclinic p2 symmetry at the stoichiometric composition. Detailed analysis of the geometry of the dendrimers accommodated in the interstitial tunnels surrounded by the SDS cylinders revealed that the dendrimer molecules were elongated into prolate ellipsoids along the long axis of the cylinders for enhancing charge matching. The degree of deformation was governed by the interplay among the electrostatic free energies and the elastic free energy associated with dendrimer deformation. The presence of monovalent salt was found to relax the dendrimer deformation due to electrostatic screening, while retaining the packing symmetry of the ribbon phase. In addition to ribbon phases, by adjusting the degree of protonation of dendrimer (dp) and the nominal binding fraction (X) of the SDS to the dendrimer, the SAXS results revealed the formation of body-centered cubic phase (BCC), nematic columnar phase (Ncol) and the other four types of 2D columnar mesophase composed of SDS columnar micelles and dendrimer accommodating within the interstitial tunnels, including hexagonal columnar phase (Colhex), simple rectangular columnar phase (Colsr), oblique columnar phase (Colob) and centered rectangular columnar phase (Colcr). Detailed analysis of the geometry of the dendrimer in the complexes manifested that the structural transition was governed by interplay among the lateral and axial deformation of dendrimer and the deformation of SDS micelle cross section for achieving effective charge matching and accommodation of the dendrimer. The present study demonstrated the power of dendrimer in directing the packing of soft cylinders via electrostatic interaction to yield a rich polymorphism of columnar mesophase for the development of functional materials.

Abstract I
摘要 III
Table of Contents V
List of Figures VII
List of Tables XIII
Chap 1. Introduction and Literature Review 1
1.1 Properties of Dendrimer 1
1.2 Self-assembly of Polymers and Colloid-like Molecules 5
1.3 Liquid Crystalline Colloids of Nanoparticles 9
1.4 Ribbon Phase in Surfactant System 13
1.5 Motivation and Overview of the Dissertation 14
Chap 2. Experimental Section 18
2.1 Materials and Preparation of Complex 18
2.2 Polarized Optical Microscope (POM) Experiment 19
2.3 Cryogenic Electron Microscopy (Cryo-TEM) Experiment 19
2.4 Small Angle X-ray Scattering (SAXS) Measurements 20
2.5 1H NMR Spectroscopy Experiment 20
Chap 3. Results and Discussion 21
3.1 Ribbon Phase of Dendrimer-Surfactant Complexes 21
3.1.1 2D Lattices of the Ribbon Phase 21
3.1.2 Analysis of Dendrimer Geometry in the Complex 32
3.1.3 Discussion on the governing thermodynamic factors of structural formation 37
3.1.4 Effect of Monovalent Salt 40
3.2 Tuning the Structure of Dendrimer-Surfactant Complexes 44
3.2.1 Lattice Structures of the Complexes 44
3.2.2 Arrangement of Dendrimer and SDS Micelle in the Complexes 57
3.2.3 A Summary of The Factors Governing the Phase Transitions 70
Chap 4. Conclusion 73
Reference 75
Appendix A. 1H NMR spectroscopy experiment for determination of actual SDS binding ratio, Xa 82
Appendix B. The actual compositions of Xn/0.5 and Xn/1.0 complexes as a function of salt concentration 87

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