本文選題：過氧化爆炸物　切入點：過氧化氫　出處：《西南科技大學(xué)》2017年碩士論文

【摘要】：近年來,恐怖爆炸襲擊事件頻發(fā),反恐防爆相關(guān)方法和技術(shù)引起了世界各國的廣泛關(guān)注。過氧化爆炸物作為新型炸藥因其原料易得、合成簡單、爆炸威力大的特點,被恐怖分子廣泛用于恐怖爆炸襲擊活動。然而,過氧化爆炸物既沒有紫外吸收也沒有熒光發(fā)射,且其化學(xué)結(jié)構(gòu)同時缺乏硝基和芳香烴基,以致其分析檢測面臨極大的挑戰(zhàn)。目前,基于熒光法的分子探針具有靈敏度高、選擇性好、操作簡單、攜帶方便等優(yōu)點,逐漸發(fā)展為爆炸物檢測領(lǐng)域的重要方法之一。過氧化爆炸物含有過氧化基團(-O-O-),而過氧化基團不穩(wěn)定,易光解產(chǎn)生過氧化氫(H2O2),且H2O2也是合成過氧化爆炸物的必要原料。通過對過氧化爆炸物的信號分子H2O2的分析檢測有望實現(xiàn)對過氧化爆炸物的有效監(jiān)測與預(yù)警。因此,本論文以對H2O2有較高選擇性的苯偶酰為識別基團,以具有光穩(wěn)定好、摩爾消光系數(shù)大等優(yōu)點的二氟化硼二吡咯甲烷(BODIPY)為熒光團,設(shè)計合成了兩種新型H2O2熒光探針4-(4-硝基苯偶�；�)-氟硼二吡咯甲烷(PBD-3)和3-(4-硝基苯偶酰基)-氟硼二吡咯甲烷(MBD-3),并表征了它們的化學(xué)結(jié)構(gòu),考察了光譜性質(zhì),探討了檢測性能。具體工作如下:(1)以3-碘苯甲酰氯和4-碘苯甲酰氯以及2,4-二甲基吡咯、對硝基苯乙炔等為起始原料,先后經(jīng)過Friedel-crafts酰基化反應(yīng)、Sonogashira偶聯(lián)反應(yīng)、Pd I2-DMSO催化氧化反應(yīng)等化學(xué)反應(yīng),設(shè)計合成了兩種新型H2O2熒光探針PBD-3和MBD-3,并借助1H NMR,13C NMR及高分辨質(zhì)譜對新型探針及相關(guān)中間產(chǎn)物的化學(xué)結(jié)構(gòu)進行了表征。(2)考察了新型熒光探針及其H2O2衍生產(chǎn)物的熒光性質(zhì)。新型探針以苯偶酰為識別基團,BODIPY為熒光團。探針PBD-3和MBD-3自身熒光很弱;當與H2O2響應(yīng)之后其熒光增強,基于d-PET機理發(fā)出很強的綠色熒光。探針及其H2O2衍生產(chǎn)物具有很好的光穩(wěn)定性,連續(xù)光照3 h,探針PBD-3和MBD-3的熒光基本保持不變,它們的H2O2衍生產(chǎn)物的熒光強度仍分別保持在92%及86%以上。(3)探討了新型探針的檢測性能。探針對H2O2具有較高的選擇性,不易受活性小分子、硝基爆炸物及硝基爆炸物的降解產(chǎn)物的干擾。探針還具有較高的靈敏度,其檢測限分別為0.9μmol/L和1.4μmol/L。(4)初步探究了新型探針PBD-3和MBD-3對H2O2蒸氣的響應(yīng)。兩種探針均可很好的響應(yīng)H2O2蒸汽,且響應(yīng)迅速靈敏。
[Abstract]:In recent years, terrorist bombing attacks occur frequently, anti-terrorist explosion-proof methods and technologies have attracted wide attention all over the world.As a new type of explosive, explosive peroxide is widely used by terrorists in terrorist attacks because of its advantages of easy availability, simple synthesis and high explosive power.However, there is no UV absorption or fluorescence emission, and the chemical structure of explosive peroxide is short of both nitro and aromatic groups, which makes the analysis and detection of explosive peroxide face great challenges.At present, the molecular probe based on fluorescence method has the advantages of high sensitivity, good selectivity, simple operation, easy to carry, and so on, and has gradually developed into one of the important methods in the field of explosive detection.The explosive peroxide contains peroxide-O-O-O, which is unstable and easy to photolysis to produce H _ 2O _ 2H _ 2O _ 2, and H2O2 is also a necessary raw material for the synthesis of explosive peroxide.By analyzing and detecting the signal molecule H2O2 of explosive peroxide, it is hopeful to realize the effective monitoring and early warning of explosive peroxide.Therefore, in this thesis, the benzyl group with high selectivity to H2O2 was used as the recognition group, and the boron difluoride dipyrrole methane (BODIPY), which had the advantages of good light stability and large molar extinction coefficient, was used as the fluorescence group.Two novel H2O2 fluorescent probes, 4-pyrrolidyl 4-fluoroboroyl-dipyrrolidine (PBD-3) and 3-pyrrolidene-fluorobenzene dipyrrolidene (MBD-3), were designed and synthesized. Their chemical structures were characterized, their spectral properties were investigated and their detection properties were discussed.The specific work is as follows: (1) starting from 3-iobenzoyl chloride, 4-iodobenzoyl chloride, 2o 4-dimethylpyrrole, p-nitrobenzoacetylene and so on, the catalytic oxidation reaction of PD I2-DMSO was successively carried out through Friedel-crafts acylation reaction and Sonogashira coupling reaction.Two novel H2O2 fluorescent probes, PBD-3 and MBD-3, were designed and synthesized. The fluorescence properties of the novel probes and their H2O2 derivatives were characterized by 1H-NMR-13C NMR and high-resolution mass spectrometry.The new probe uses benzoyl as the recognition group and BODIPY as the fluorescence group.The fluorescence of the probe PBD-3 and MBD-3 is very weak, and the fluorescence of the probe increases when it responds to H2O2, and it emits a strong green fluorescence based on the mechanism of d-PET.The probe and its H2O2 derivatives had good photostability. The fluorescence of probe PBD-3 and MBD-3 remained unchanged after 3 h continuous illumination.The fluorescence intensity of their H2O2 derivatives remained at 92% and over 86% respectively.The probe has high selectivity to H2O2 and is not easily interfered by the degradation products of active small molecules, nitro explosives and nitro explosives.The detection limits of the probe were 0.9 渭 mol/L and 1.4 渭 mol / L 路L ~ (4), respectively. The response of the new probe PBD-3 and MBD-3 to H2O2 vapor was preliminarily investigated.Both probes can respond well to H2O2 steam, and the response is rapid and sensitive.
【學(xué)位授予單位】：西南科技大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TQ560.72;O657.3

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