臺灣博碩士論文加值系統

利用2,4-二硝基苯肼(2,4-dinitrophenylhydrazine, DNPH)做為量測醛類的衍生試劑為最常見及廣泛應用的分析方法，通常在酸性催化衍生下以高效率液相層析儀 (high performance liquid chromatography, HPLC)搭配紫外光可見光偵測器(UV/Vis detector)量測在360 nm處DNPH衍生物(hydrazone)的光譜吸收；我們藉由探討不同溫度下衍生反應的平衡常數，及衍生最佳pH值與DNPH質子化的關係對此衍生反應的機制有更進一步的了解，發現此衍生反應在室溫下有最高的反應平衡常數，DNPH質子化的平衡常數K1= 46.8 M-1。過去的研究發現二價銅 （Cu(II)）易與DNPH上的聯氨(Hydrazine)反應，進而造成分析方法的干擾，然而Cu(II)對此衍生反應的影響除了對DNPH造成分解外，Cu(II)與醛類的斐林反應(Fehling reaction)及Cu(II)對衍生物穩定性干擾，也都為影響此反應的因素，本篇研究目的為釐清Cu(II)對衍生反應造成的影響由何者所貢獻，並藉由加入EDTA(Ethylene dinitrilotrteaacetic acid) 做為Cu(II)的抑制劑，發現在加入適量的EDTA情況下可以有效降低Cu(II)對此反應的干擾。

目錄
中文摘要.........................................................................................................................I
英文摘要.......................................................................................................................II
謝誌..............................................................................................................................III
目錄..............................................................................................................................IV
圖目錄..........................................................................................................................VI
表目錄........................................................................................................................VII

第一章 前言................................................................................................................1
1.1 簡介..................................................................................................................1
1.2 研究目的及動機..............................................................................................2
第二章 文獻回顧......................................................................................................3
2.1 醛的測量方法….................................................................................………3
2.1.1. 直接進樣法....................................................………............................3
2.1.2. 衍生法........................ ...............................................................………3
2.2 銅的介紹............................ ....................................................…........………6
2.3 醛與DNPH........ ....................................................……....................………7
2.4 DNPH的反應............................ ....................................................…………9
2.5 DNPH的應用............................... ....................................................………11
2.6 斐林反應. ....................................................................................………12
第三章 實驗方法......................................................................................................13
3.1 實驗裝置.........................................................................................................13
3.1.1. 紫外光可見光譜儀（UV/Vis spectrometer）.....................................13
3.1.2. 高效率液相層析儀（HPLC）..................................... ..........................13
3.1.3. 其他儀器..............................................................................................14
3.2 實驗計算軟體（MINTEQ）............................................................................14
3.3 實驗藥品..................................... ...................................................................15
3.2.1. 藥品..................................... ... ............................................................15
3.2.2. 母液配置..................................... ............................ ...........................16
3.4 分析流程........................................ .......................... .....................................18
3.4.1. 以UV/Vis觀察DNPH及DNPH衍生物之光譜特性......................18
3.4.2. 醛的分析..................................... ........................................................18
3.4.3. 酸的分析................................. ...................... .....................................18
3.4.4. 斐林反應的測試..................................... .........................................19
3.4.5. 實驗流程圖..................................... ..................................... ..............19
第四章 結果與討論…..............................................................................................20
4.1 衍生反應的最佳化..................................... ........................ ..........................20
4.1.1. HPLC分析條件..................................... .............................................20
4.1.2. 溫度對衍生反應的影響化................................... ..............................21
4.1.3. 反應平衡常數的探討..........................................................................23
4.1.4. DNPH質子化與衍生pH值................................................................26
4.1.5. Cu(II)及EDTA的影響.....................................................................29
4.1.6. 衍生條件最佳化..................................... .......................... .................32
4.1.7. 反應機制的探討...............................................................................33
4.2 斐林反應的測試..................................... ........... ......................................34
4.3 衍生物的穩定性測試..................................... ....... .......................................35
第五章 結論與展望..………………………………………..……………………..38
參考文獻......................................................................................................................39
附錄I 醛之檢量線............................................................ ........................................i
附錄II 各個醛在不同溫度下反應常數....................................................................ii
附錄III 各個醛在不同pH值下改變Cu(II)、EDTA濃度及衍生時間……….........iii

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