臺灣博碩士論文加值系統

本論文報導了設計及合成生物體內重要受質的氫鍵受體，在受體的設計上著重在中性合成受體，藉由氫鍵對受質產生強且具高選擇性的有效辨識，這些受質包括磷酸根離子、醣類及三胜月太分子，其中磷酸根離子受體具有類似四面體的構形，與磷酸根離子形成化學計量比為1:1的氫鍵錯合物，並具有高度的辨識能力與可修飾性，鍵結的強弱除了與陰離子本身的鹼度有關外，受體分子的幾何構形、第二層醯胺鍵的酸度及柔軟度，也扮演著極為重要的角色。在受體分子上引入蒎螢光團後，透過單體與激發態複合體螢光放光的消長現象，對磷酸根離子產生靈敏的感應效果，整個感應機制可被進一步應用於含水溶劑中，對二磷酸根離子進行感測，感測的結果與陰離子的鹼度及離子的大小有關。
受體分子BPN具有daad的氫鍵排列可與醣甘受質產生化學計量比為1:1的互補性氫鍵鍵結模式，鍵結強度依序是a-D-甘露醣醣甘> b-D-葡萄醣醣甘> a-D-葡萄醣醣甘> b-D-半乳醣醣甘> b-D-果醣醣甘> b-L-海藻醣甘≒b-D-核醣醣甘，鍵結的強度與醣甘分子的幾何構形與羥基的多寡有絕對的關聯，而受體分子與受質間可產生多重氫鍵的數目與強弱也是決定性的因素之一。整體而言，BPN對於b-D-葡萄醣與a-D-甘露醣醣甘具有較好的辨識能力，由氫核磁共振光譜推論的鍵結模式與多重氫鍵的重要性，可由理論計算模擬受體BPN/醣錯合物的構形及鍵結方式得到支持。此外，BPN本身可以當成一個本質性的發光團，透過與醣甘分子間多重氫鍵的形成，加強了電荷轉移的機制，對b-D-葡萄醣醣甘產生高選擇性的感應效果，由於受體與所形成錯合物的螢光最大放光波長約有60 nm差異，再配合錯合物的螢光放光的量子產率高達0.25，使受體BPN更具潛在的應用價值。
對於三胜月太受質，我們利用具辨識端（環醯胺）及感應端（釕（II）二口比啶錯合物）的受體分子，以組合化學的方式進行受質的篩選，初步的結果發現受體對三胜月太分子的辨識選擇性地集中在有Gly與D-Ala的胺基酸序列上，並可看出受體對三胜月太分子具有鏡像選擇性的效果。

This thesis presents the design and synthesis of nitrogen-containing compounds as the hydrogen-bond receptors for biologically important substrates, such as phosphates, carbohydrates and tripeptides. The structural cleft of phosphate receptor is established by incorporating four additional amido groups onto pyridine 2,6-biscarboxamide to provide a pseudo-tetrahedral cleft to hold phosphates in 1:1 complexation stoichiometry.
The receptor with 1-pyrenylmethyl groups serves as a selective chemosensor for phosphates with unique recognition and sensing properties. The sensing mechanism appears to have phosphate ion encapsulated into the core of cleft via six hydrogen bonds, which disturbs the equilibrium between monomer and excimer fluorescence of pyrenyl moieties before and after complexation. This concept can be further applied in sensing pyrophosphate ion in water-containing solvents.
BPN with daad hydrogen-bonding relay forms complexes with glycosides in 1:1 complexation. The binding trend among various saccharides is as follows: α-D-mannoside > β-D-glucoside > α-D-glucoside > β-D-galactoside > β-D-fructoside >β-L-fucoside≒β-D-ribofuranoside. The formation of multiple hydrogen-bonding complex adopts a rigid conformation to enhance fluorescence. More importantly, through themultiple HB effect the unusual push-pull daad relay conjugated through the ethynyl bridge further induces the p-electron delocalization of the intrinsic conjugated chromophore in BPN. These combinations lead to the operation of the multiple hydrogen-bonds induced charge transfer effect, resulting in drastic alternation on both UV-vis and fluorescence properties. The high affinity of BPN for β-D-glucoside, in combination with the high quantum yield and well-separated complex fluorescence, demonstrates its future suitability in developing glucose sensor.
The amide-based receptor was designed and synthesized. The macrocyclic amides and ruthenium (II) bipyridyl moieties serve as recognition and sensing unit, respectively. A combinatorial approach is used to examine the recognition of this receptor with a library of tripeptides. The preliminary screening results indicate that the receptor binds the tripeptides having Gly and D-Ala amino acid residues.

目錄···························I
圖目錄··························III
表目錄····················· VIII
簡稱用語對照表······················IX
中文摘要·························X
英文摘要·························XIII
壹、 緒論·········· 1
貳、 結果與討論··················· 26
第一部分：磷酸根離子受體················· 26
一、 前置研究···················· 28
二、 取代基效應····················40
三、 磷酸根離子螢光化學感應器的研發··········51
四、 其他可能的應用··················70
第二部分：醣類分子受體·················· 81
一、 受體分子的合成與結構鑑定·············82
二、 鍵結能力的評估·············· 87
三、 醣甘螢光化學感應器的研發·············98
四、 其他合成受體的研發················115
五、 感應機制的探討··················128
第三部分：三胜月太分子受體················· 137
一、 受體分子的合成··················138
二、 利用組合式化學進行三胜月太分子的篩選········146
參、 綜合結論·····················156
肆、 實驗部分·····················158
伍、 參考文獻·····················244
陸、 附錄·······················256

伍、參考文獻
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