具自組裝功能基團的紫質衍生物設計與合成及其形成之奈米微結構研究

Design and Synthesis of Porphyrin Derivatives with Self-Assembled Functional Groups and Characterization of their Nanostructures

郭明承(Ming-Cheng Kuo)

指導教授 ： 汪根欉

國立臺灣大學/理學院/化學研究所/博士(2012年)

https://doi.org/10.6342/NTU.2012.02690

摘要

我們設計與合成了具有不同作用力的自組裝官能基團之紫質衍生物，研究分子結構與其自組裝微結構的相對關係，利用掃描式與穿透式電子顯微鏡等工具鑑定紫質化合物自組裝的奈米結構。T-dicZnP具烷類疏水性自組裝基團，自組裝形成一維柱狀結構，藉由高極性甲醇增加疏水性作用力強度，則形成二維片狀結構。T-p-ditdiuZnP具雙縮脲官能團經由自組裝形成奈米球結構，且奈米球的形成與否不太會受四氫呋喃與甲醇溶劑組成影響。T-p-dicdiuZnP分子同時具有T-dicZnP與T-p-ditdiuZnP的自組裝官能基團，高極性條件下疏水性作用力主導自組裝而形成一維柱狀結構。反之，在低極性條件下由親水性作用力主導自組裝而形成奈米球結構。
藉由改變雙縮脲基團與紫質核心的相對位置，研究分子結構與自組裝結構的相對關係。我們設計了T-m-ditdiuZnP、T-m-dicdiuZnP、T-p-ditdiuZnP和T-p-dicdiuZnP等分子，四個異構物在醇類溶劑皆形成奈米球結構，在非醇類溶劑則有不同的奈米結構與分子結構有密切關係。

關鍵字

紫質 ； 自組裝 ； 氫鍵 ； 雙縮脲

並列摘要

We design a series of porphyrin derivatives with self-assembly motifs to study the correlation between molecular structure and self-assembled nanostructure. We use scanning electron microscopy and transmission electron microscopy as tools to identify the self-assembled structures of porphyrin derivatives. It is observed that the formation of different nano-morphologies such as nano-rod or hollow sphere can be manipulated either by the structural features and/or solvent compositions. In this regard, T-dicZnP with hydrophobic substitutions forms one-dimension rods, T-p-ditdiuZnP with hydrophilic substitutions gives hollow spheres. T-p-dicdiuZnP possessing the substituents of T-dicZnP and T-p-ditdiuZnP can interchange the nanostructure between one-dimension rods and hollow spheres through the control of solvent composition.
We design a series of porphyrin isomers to map the correlation between molecular structure and self-assembled nanostructures. The porphyrin isomers form hollow spheres in protic solvent, but they give distinct nano-morphologies in aprotic solvent.

並列關鍵字

porphyrin ； self-assembly ； hydrogen bond ； biuret

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