臺灣博碩士論文加值系統

將欲分析之化合物區分為兩類：(1)有兩個可質子化氮原子存在，例如：2-StQ-NMe2、2-StP-NMe2等系列的化合物；(2)只有一個可質子化氮原子存在－氮,氮-二甲基胺，例如：2-StT-NMe2與2-StN-NMe2等系列的化合物。
奎林環上氮原子的鹼度較大，若質子化作用在此官能基，吸收圖譜與放射圖譜皆呈現相當大的紅位移；反之，分子內電荷轉移(ICT)的特性使得氮,氮-二甲基的鹼度變小，若質子化作用在此官能基，圖譜則反而呈現更大的藍位移。
由於donor group在激發態因分子內電荷轉移的發生而使其鹼度下降，因此在基態質子化的物種可能因激發態鹼度改變而產生激發態去質子化。我們利用UV光譜儀評估各化合物的pKa值，並使用Forster Cycle測得各官能基在激發態的鹼度( pKa*)。
ΔpKa (pKa*﹣pKa)值較大的2-StQ-NMe2、2-StP-NMe2等系列化合物，在激發態時進行去質子化的機制；若ΔpKa*值較小的2-StT-NMe2與2-StN-NMe2在激發態時無法產生去質子化的機制。而只能產生激發態去氫鍵化的機制，此篇論文利用不同具ICT化合物來探索激發態去質子化與去氫鍵化反應的細節。
最後將各化合物在水系統中包埋於兩種不同內徑的環糊精(α-與HP-β-CD)，以便將觸角延伸至偵測生物體的應用方面。
由於具ICT化合物所處周圍環境，會明顯地影響此化合物光物理表現，於是利用這些特殊的光譜位移，便可推測出周圍環境的介質極性；此方面的研究可作為生化感測器上的應用。例如：極性感測器、氫鍵感測器與酸鹼感測器等。

To understand the influence of substituents and solvent effect on intramolecular charge transfer (ICT), absorption and emission spectra were measured for several derivatives of 2-styrylquinoline (2-StQ), 2-styrylpyridine (2-StP), 2-styrylthiophene (2-StT), and p-N, N-dimethylamino-2-styrylnaphthalene (2-StN-NMe2) system.
A strong donor, such as an N, N-dimethylamino group can produce an ICT compound in these systems, and the excited state dipole moments were measured using a solvatochromic method.
The excited-state reaction of push-pull styryl system was studied in this work. The influence of hydrogen bonding (HB) and protonation on an intramolecular charge transfer (ICT) compound, such as compounds of 2-StP-NMe2, 2-StQ-NMe2, 4-StQ-NMe2 and 4-StP-NMe2 etc.
The absorption and emission spectra for push-pull styryl system were studied in aprotic dichloromethane and at various acid concentrations. Monoprotonated or doubly protonated forms are present depending on the acid concentration. Excited state deprotonation of the doubly protonated form is observed in aprotic dichloromethane solvent for compounds with two protonation sites. Protonation and hydrogen bonding at acceptor site show red shift in absorption maxima. Interaction at donor site gives the opposite result.
Compounds of 2-StQ-NMe2, 2-StP-NMe2, 4-StQ-NMe2, and 4-StP-NMe2 etc. possess a sufficiently large acidity change for the proton transfer process to occur. For compounds 2-StT-NMe2 and 2-StN-NMe2 the acidity change is too small to induce the proton transfer process.
A new type of excited-state de-hydrogen bond (ESDHB) process was observed in this study. It is possible to explore the polarity and HB effect of solvent simultaneously by using the ESDHB mechanism.
The sensitivity for various compounds in exploring the polarity and hydrogen bond of the medium was compared with the Stokes shift in different solvent.
The influences of rigid medium to ICT were also studied for several compounds. We did not find any influence of viscosity to ICT even in iced ethylene glycol. The inclusion complex between α-cyclodextrin or HP-β-cyclodextrin with different compounds were recorded for studying the application of theses compounds in bio-system. The dielectric constant values of the α-cyclodextrin or HP-β-cyclodextrin cavities probed by different compounds are between 5.0 to 10 and 15 to 25 respectively because of the difference in size of the probe molecule inside the cavity.

中文摘要 …………………………………………………… 6
英文摘要 …………………………………………………… 7
研究報告之架構、動機與目的 …………………………… 9
第一章 光譜機制與反應機制介紹…………………………10
第二章 氫鍵結與質子化……………………………………19
第三章 溶劑效應……………………………………………23
第四章 pKa值 ……………………………………………26
第五章 環糊精的結構與其物理性質………………………29
第六章 結果與討論─實驗方法與原理……………………32
第七章 結果與討論…………………………………………38
第八章 結論…………………………………………………64
第九章 實驗…………………………………………………66
第十章 參考文獻……………………………………………68
第十一章 圖…………………………………………………72
第十二章 表……………………………………………… 131
第十三章 附錄(各化合物之H-NMR圖譜)………………154

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