本論文深入探討十二烷苯磺酸鈉(DBSNa)界面活性劑與不同質子化程度(dp)的polyamidoamine (PAMAM) G3和G4樹狀分子靜電錯合物的自組裝結構，經由同步輻射小角度X光散射(SAXS)的解析，觀察到錯合物形成了多種有序的奈米結構，導致液晶相的形成。
首先，對於PAMAM G3樹狀分子的較低質子化程度（dp = 0.3 ~ 0.35）錯合物進行探討。在低的DBSN結合比例(Xn)值下，SAXS曲線表明該錯合物形成了二維六角柱狀相(Colhex)，其中DBSNa形成圓柱狀胞排列在二維六角晶格中，而樹狀分子則鑲嵌在柱狀微胞中間的空隙中。在高的Xn值下，觀察到奇特的散射圖譜，其中有兩組六角繞射，表明形成了蜂巢狀超晶格結構。隨著PAMAM G3樹狀分子的質子化程度增加（dp≧0.7），錯合物形成了平面層狀結構，其中極性層和非極性層交替堆疊。這種結構轉變是為了達到更好的電荷匹配效果，導致柱狀微胞更進一步融合，形成了平板層。
本研究進一步探討質子化程度不同的PAMAM G4 樹狀分子與DBSNa的靜電錯合物。隨著Xn的增加，錯合物的結構由Colhex相轉變為具有中心矩形堆疊的柱狀(Colcr)相。而在較高的dp值時，形成了簡單矩形晶格結構。此外，在更高的dp值下，觀察到了更複雜的散射圖譜，被歸因於一個二維與三維單斜晶混成超晶格結構的形成。
總體而言，這項研究揭示了PAMAM G3和G4樹狀分子與DBSNa錯合物形成的多種有序奈米結構，並深化了對錯合機制的理解。這些結果對設計和合成新型功能材料具有重要的參考價值。

This thesis delves into the self-assembled structures of electrostatic complexes formed between sodium dodecyl benzene sulfonate (DBSNa) surfactant and polyamidoamine (PAMAM) G3 and G4 dendrimers with different degrees of protonation (dp). Through the use of synchrotron small-angle X-ray scattering (SAXS), a variety of ordered nanostructures formed by the complexes were identified, leading to the formation of mesomorphic phases.
To begin, the complexes of PAMAM G3 dendrimers with lower degrees of protonation (dp = 0.3 ~ 0.35) were explored. At lower DBSNa binding ratios (Xn), the SAXS curves indicated the formation of a two-dimensional (2D) hexagonal columnar phase (Colhex), where DBSNa molecules formed cylindrical micelles packed into a 2D hexagonal lattice, and the dendrimer molecules were embedded in the interstitial regions between the micelles. At the higher Xn values, distinct scattering patterns featuring two sets of 2D hexagonal diffractions were observed. This scattering pattern was attributed to the formation of a honeycomb superlattice structure composed of DBSNa and the interconnected dendrimer columns cooperatively organized in a hexagonal lattice. As the degree of protonation of PAMAM G3 dendrimers increased (dp≧0.7), the complexes adopted a planar layered structure, with alternating polar and non-polar layers. This structural transition occurred to achieve better charge matching, leading to further fusion of the cylindrical micelles into plate-like layers.
The study further investigated electrostatic complexes between PAMAM G4 dendrimers with varying degrees of protonation and DBSNa. With increasing Xn, the structure of the complexes transitioned from a Colhex phase to a centered rectangular columnar phase (Colcr). At higher dp values, a simple rectangular lattice structure was formed. Moreover, at even higher dp values, more complex scattering patterns were identified and attributed to the formation of a hybrid superlattice structure combining two-dimensional and three-dimensional monoclinic lattices.
In conclusion, this study has revealed a range of ordered nanostructures formed by complexes of PAMAM G3 and G4 dendrimers with DBSNa, which deepens the understanding of the complexation mechanism. These findings hold significant value for the design and synthesis of novel functional materials.

章節目錄
(一) 背景與文獻回顧 16
1.1 前言 16
1.2 樹枝狀高分子dendrimer之文獻 17
1.3 兩性界面活性劑(surfactant)之相關文獻 24
1.4 DBSA-dendrimer自組裝研究結構探討 29
1.5 SDS-dendrimer自主裝研究結構探討 36
1.6 研究動機與目的 47
(二) 樹枝狀聚合物與界面活性劑之研究方法與工具 49
2.1錯合物樣品與材料之準備：PAMAM dendrimer(G3、G4)、界面活性劑DBSNa 49
2.1.1 PAMAM dendrimer質子化程度之調控 49
2.1.2 PAMAM dendrimer與界面活性劑錯合比例之調控 50
2.2 實驗結構分析之原理 51
2.2.2 小角度散射(SAXS, Small Angle X-ray Scattering)原理分析 51
2.2.2 偏光顯微鏡(POM, Polarized Optical Microscope)原理 54
(三) 結果與討論 55
3.1 DBSNa – G3 PAMAM dendrimer之錯合物研究探討 56
3.2 DBSNa – G4 PAMAM dendrimer之錯合物研究探討 76
(四) 總結 85
(五) 相關文獻 86

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