过氧化爆炸物信号分子检测用新型荧光探针的构筑及性能研究

发布时间：2018-04-03 18:44

本文选题：过氧化爆炸物　切入点：过氧化氢　出处：《西南科技大学》2017年硕士论文

【摘要】：近年来,恐怖爆炸袭击事件频发,反恐防爆相关方法和技术引起了世界各国的广泛关注。过氧化爆炸物作为新型炸药因其原料易得、合成简单、爆炸威力大的特点,被恐怖分子广泛用于恐怖爆炸袭击活动。然而,过氧化爆炸物既没有紫外吸收也没有荧光发射,且其化学结构同时缺乏硝基和芳香烃基,以致其分析检测面临极大的挑战。目前,基于荧光法的分子探针具有灵敏度高、选择性好、操作简单、携带方便等优点,逐渐发展为爆炸物检测领域的重要方法之一。过氧化爆炸物含有过氧化基团(-O-O-),而过氧化基团不稳定,易光解产生过氧化氢(H2O2),且H2O2也是合成过氧化爆炸物的必要原料。通过对过氧化爆炸物的信号分子H2O2的分析检测有望实现对过氧化爆炸物的有效监测与预警。因此,本论文以对H2O2有较高选择性的苯偶酰为识别基团,以具有光稳定好、摩尔消光系数大等优点的二氟化硼二吡咯甲烷(BODIPY)为荧光团,设计合成了两种新型H2O2荧光探针4-(4-硝基苯偶酰基)-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),并表征了它们的化学结构,考察了光谱性质,探讨了检测性能。具体工作如下:(1)以3-碘苯甲酰氯和4-碘苯甲酰氯以及2,4-二甲基吡咯、对硝基苯乙炔等为起始原料,先后经过Friedel-crafts酰基化反应、Sonogashira偶联反应、Pd I2-DMSO催化氧化反应等化学反应,设计合成了两种新型H2O2荧光探针PBD-3和MBD-3,并借助1H NMR,13C NMR及高分辨质谱对新型探针及相关中间产物的化学结构进行了表征。(2)考察了新型荧光探针及其H2O2衍生产物的荧光性质。新型探针以苯偶酰为识别基团,BODIPY为荧光团。探针PBD-3和MBD-3自身荧光很弱;当与H2O2响应之后其荧光增强,基于d-PET机理发出很强的绿色荧光。探针及其H2O2衍生产物具有很好的光稳定性,连续光照3 h,探针PBD-3和MBD-3的荧光基本保持不变,它们的H2O2衍生产物的荧光强度仍分别保持在92%及86%以上。(3)探讨了新型探针的检测性能。探针对H2O2具有较高的选择性,不易受活性小分子、硝基爆炸物及硝基爆炸物的降解产物的干扰。探针还具有较高的灵敏度,其检测限分别为0.9μmol/L和1.4μmol/L。(4)初步探究了新型探针PBD-3和MBD-3对H2O2蒸气的响应。两种探针均可很好的响应H2O2蒸汽,且响应迅速灵敏。
[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.
【学位授予单位】：西南科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ560.72;O657.3

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