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檢測神經(jīng)毒劑類似物化學傳感器的合成及應用

發(fā)布時間:2018-05-07 12:06

  本文選題:喹啉 + 沙林毒氣; 參考:《中國科學技術大學》2017年碩士論文


【摘要】:化學戰(zhàn)爭毒劑(CWAs)是對在戰(zhàn)爭或者相關的軍事行動中用于傷害,殺害或者使敵人癱瘓的所有具有毒性的化學物質的統(tǒng)稱,主要包括糜爛性毒劑,神經(jīng)毒劑,窒息性毒劑和窒息劑。這些戰(zhàn)爭毒劑中以神經(jīng)毒劑(NAs)最為臭名昭著。盡管現(xiàn)代戰(zhàn)爭中已經(jīng)禁止使用這些毒劑,但仍然有恐怖分子利用它們對平民發(fā)動攻擊。因此,發(fā)展一種能夠快速有效檢測神經(jīng)毒劑的方法對預防此類事件的發(fā)生有重大意義。在第二章中,以6-氨基-2-甲基喹啉為母體,根據(jù)分子內電荷轉移(ICT)機理設計合成了多種化學傳感器,用于檢測一種神經(jīng)毒劑類似物——氯磷酸二乙酯(DCP)。傳感器的設計思路是將分子上的吡啶環(huán)結構同時作為反應位點和電子受體,通過DCP的催化水解過程,生成質子化的傳感器,從而產(chǎn)生出更強的ICT過程,最終導致傳感器分子的顏色以及熒光發(fā)生變化。根據(jù)氨基處取代基的不同,控制傳感器反應前后的ICT過程強弱來改變傳感器的反應性能,最后選擇出性質最好的傳感器作進一步研究。通過對傳感器反應的核磁跟蹤以及控制實驗,我們驗證了所提出的傳感機理。由于氣相檢測相對于液相檢測更具有應用價值,我們將選出的傳感器負載到高聚物上制作成膠片進行氣相實驗,其中包括在液相中最普遍的選擇性實驗和當量實驗,這些研究表明該傳感器具有很好的應用潛力。在第三章中,為了提高傳感器對DCP的檢測效率,我們對6-氨基-2-甲基喹啉的甲基進行修飾。通過簡單的兩步反應將甲基轉化為肟羥基,之后研究所選擇的三種傳感器的傳感性質;趯鞲衅鞣磻暮舜鸥櫼约皩Ψ磻a(chǎn)物進行高分辨質譜分析,我們驗證了所提出的傳感機理。挑選出性質最好的傳感器進一步進行氣相實驗。相對于之前所合成的甲基取代傳感器,肟羥基取代的傳感器仍然具有良好的選擇性和敏感性,并且在氣相檢測中對酸性蒸氣具有更好的區(qū)分性。
[Abstract]:The chemical warfare agent CWAsis a generic term for all toxic chemicals used in war or related military operations to harm, kill, or paralyze the enemy, including erosive agents, nerve agents, asphyxiating agents, and asphyxiating agents. Of these war agents, the nerve agent NAsis the most notorious. Although the use of these agents has been banned in modern warfare, they are still used by terrorists to attack civilians. Therefore, it is of great significance to develop a rapid and effective method for the detection of nerve agents. In the second chapter, using 6-amino-2-methylquinoline as the parent, several chemical sensors were designed and synthesized according to the intramolecular charge transfer (ICTI) mechanism for the detection of a nerve agent analogue, diethyl chlorophosphate (DCPP). The design idea of the sensor is to take the pyridine ring structure on the molecule as the reaction site and the electron receptor at the same time. Through the catalytic hydrolysis process of DCP, the sensor will be protonated, which will produce a stronger ICT process. Ultimately, the color and fluorescence of the sensor molecules change. According to the difference of amino substituents, the ICT process before and after the reaction is controlled to change the performance of the sensor. Finally, the best sensor is selected for further study. The proposed sensing mechanism is verified by nuclear magnetic field tracking and control experiments. Because gas phase detection is more valuable than liquid phase detection, we load the selected sensor onto polymer to make film for gas phase experiment, which includes the most common selective experiment and equivalent experiment in liquid phase. These studies show that the sensor has good application potential. In chapter 3, in order to improve the detection efficiency of DCP, we modify the methyl of 6-amino-2-methylquinoline. The methyl was converted to oxime hydroxyl group by a simple two step reaction, and the sensing properties of the three sensors were studied. Based on the NMR tracking of the sensor reaction and the analysis of the reaction products by high resolution mass spectrometry, the proposed sensing mechanism is verified. The best sensors are selected for further gas phase experiments. Compared with the previously synthesized methyl substituted sensors, the Oxime hydroxyl substituted sensors still have good selectivity and sensitivity, and they are more sensitive to acid vapor in gas phase detection.
【學位授予單位】:中國科學技術大學
【學位級別】:碩士
【學位授予年份】:2017
【分類號】:E9392;TP212.2

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