合成具有化學受體的規則樹枝狀高分子應用於螢光感測

Synthsis of Dendritic Polymers Functionalized with Chemoreceptors for Fluorescent Sensors

内部錦(Nishiki Uchibe)

指導教授 ： 鄭如忠

國立臺灣大學/工學院/高分子科學與工程學研究所/碩士(2019年)

https://doi.org/10.6342/NTU201900683

摘要

本研究利用高效率的交替式反應，合成出具有光化學受體的樹枝狀 poly(urea/maloamide)s 結構，並應用於螢光感測用途。首先透過合成具有高度反應 選擇性雙官能基的 4-isocyanato-4’ (3,3-dimethyl-2,4 -dioxoazetidino)diphenylmethane（IDD）做為構築單元，再分別與具羥基和氨基等活性氫官能基的化合物進行反應，在溫和條件、無催化劑與高產率精準合成出具有兩種不同化學反應性之規則樹枝狀高分子。透過反應優化與設計，並成功免除了傳統樹枝 狀高分子保護/去保護，或是活化/去活化等等繁瑣之合成方法，成功合成出外圍含 溴官能基與核心為aztidine-2,4-dione 官能基的之雙官能基poly(urea/maloamide)s 樹 枝狀高分子。此外，由於光化學受體 dipicolylamine 之二級胺和 aztidine-2,4-dione之間具有反應性，透過測試反應優化實驗條件後，成功以一鍋化合成方法對溴官能 基進行取代反應而不產生 aztidine-2,4-dione 官能基的開環加成反應，在 1.5 代的雙官能基 poly(urea/maloamide)s 樹枝狀高分子上能夠展現出將近 100%的反應選擇性。以上述反應為基礎，一系列具多個化學感受器的 poly(urea/maloamide)s 樹枝狀高分 子能夠合成出來，並應用於光化學感測器應用。

關鍵字

樹枝狀高分子 ； 高分子後修飾 ； poly(urea/maloamide)s ； 光化學感測

並列摘要

A series of dentritic poly(urea/malonamide)s functionalized with chemoreceptors were prepared through an efficient iterative synthesis for fluorescent sensors. The dendrons were first prepared from the dual functional building block 4-isocyanato-4’ (3,3-dimethyl-2,4 -dioxoazetidino)diphenylmethane (IDD) as the starting materials. Throught, the use of IDD and active hydrogene such as hydroxyl and amino group, a series of well-defined bifunctional poly(urea/maloamide)s dendrons with peripheral bromo moieties were realized under mild condition without resorting to painstaking protection-deprotection or activation methodology. In the model study between dipicolylamine and aztidine-2,4-dione, the results revealed the chemical activity of the secondary amine for dipicolylamine, leading to an unusual synthetic strategy to achieve the dendritc chemoreceptors. Consequently, these chemoreceptors-functionalized dendrons would be able to exhibit specific metal ion affinity for applications of fluorescent sensors.

並列關鍵字

dendrons ； post-functionalization ； chemosensors

參考文獻

1. Tomalia, D. A.; Baker, H.; Dewald, J.; Hall, M.; Kallos, G.; Martin, S.; Roeck, J.; Ryder, J.; Smith, P., A new class of polymers: starburst-dendritic macromolecules. Polymer Journal 1985, 17 (1), 117.

2. Tomalia, D. A., Birth of a new macromolecular architecture: dendrimers as quantized building blocks for nanoscale synthetic polymer chemistry. Progress in Polymer Science 2005, 30 (3-4), 294-324.

3. Lee, C. C.; MacKay, J. A.; Fréchet, J. M.; Szoka, F. C., Designing dendrimers for biological applications. Nature biotechnology 2005, 23 (12), 1517.

4. Liang, C.; Fréchet, J. M., Applying key concepts from nature: transition state stabilization, pre-concentration and cooperativity effects in dendritic biomimetics. Progress in polymer science 2005, 30 (3-4), 385402.

5. Liang, C. O.; Fréchet, J. M., Incorporation of functional guest molecules into an internally functionalizable dendrimer through olefin metathesis. Macromolecules 2005, 38 (15), 6276-6284.