【作者】 刘玉；

【导师】 张同来；

【作者基本信息】 北京理工大学 ， 物理化学， 2014， 博士

【摘要】 以苦味酸（PA）、斯蒂酚酸(TNR)和三硝基均苯三酚(TNPG)为主的多硝基多酚及其配合物，因其热感度和火焰感度高、易发火、并且输出具有高能量火焰的特点，已经被广泛应用于点火药的设计和生产。随着兵器行业、民爆行业中大量使用硝基酚为原料和中间体，越来越多的有害物质被排放、进入水域或留存于土壤中，并通过食物链的富集，进入人体，其中有一些硝基酚类物质具有高度的致癌、致畸、致突变作用，将对人类产生不可估量的危害。因此，发展以兵器行业生产和使用的多硝基多酚为主要研究对象，重点建全和完善环境样品中硝基酚有害多残留分析技术，监督控制环境污染程度，已成为重要的研究方向。本论文的主要研究内容是针对兵器行业生产和使用的多硝基多酚的检测问题，研究了快速、经济和有效的前处理技术，提高检测灵敏度的仪器分析技术，用于复杂基体样品中多种硝基酚残留的检测，并进行了相关的不同色谱柱间吸附理论研究和质谱裂解规律分析。论文的主要研究内容和取得的成果如下：1.首次建立了完善的超声波辅助萃取气相色谱质谱法(GC MS)测定环境水、地面沉积物、土壤中硝基酚类多残留的分析方法。本方法实现了三硝基一酚、三硝基二酚等8种硝基酚的同时测定方法，克服了多种硝基酚的结构、性质差异带来的难分离、不稳定的特点，拓宽了气相色谱质谱在同时测定多硝基酚类物质的检测领域，为同类物质的气质检测提供了可行分析。采用此方法测定水、土壤、地面沉积物中的硝基酚类并做添加回收实验验证，结果表明方法准确、实用，对于环境样品中硝基酚类多残留痕量化合物的测定效果良好。通过优化了前处理提取方法和仪器分析条件，8种硝基酚类分别在0.010～5.0mg/kg浓度范围内呈线性关系，相关系数0.9909，检出限分别为0.010～0.050mg/kg；平均回收率为80.6%～105.4%之间，相对标准偏差为3.4%～10.8%。2.首次将快速、简单、经济的Bond Elut Plex固相萃取前处理方法用于环境中多种硝基酚类有害残留的分析中。方法采用响应曲面实验设计方法和理想函数方程，对前处理技术中的吸附基体和洗脱溶剂因素、以及其相互作用对回收率影响进行了研究和评估。该方法选择新型的固相萃取柱应用于多硝基酚类物质的提取和净化，增强了对硝基酚类不同极性广泛的适应性，有效提高了回收率和分析效率。利用本方法处理后的样品，色谱图杂质干扰少，基线平稳，可达到完全忽略基质效应的影响效果。而且方法可自动化大批量处理样品，较其他前处理方法充分体现了实用性和先进性。Bond Elut Plex固相萃取前处理方法在回收率和基体净化之间获得最佳平衡点的前处理条件是：样品采用Bond Elut Plex固相萃取柱净化，上样5.0mL，并最终用5.0mL乙腈:四氢呋喃(4: l)洗脱，洗脱液浓缩进色谱分析。3.建立了生产环境样品中同时测定14种硝基酚类化合物的固相萃取超高效液相色谱分析方法，首次将14种不同极性硝基酚类化合物在同一色谱条件下实现基线分离。本方法选择实验室普及的通用仪器和特异性色谱分离柱，首次将强极性、热不稳定、难分离检测的三硝基间苯三酚等多硝基多酚类物质同其他多种硝基酚在同一条件实现分离、测定，达到了检测范围全面、快捷、稳定、准确的方法标准，能够满足环境水体、地面沉积物、土壤等环境样品中痕量多硝基酚类污染物检测的要求，可作为常规的检测方法应用于生产环境中痕量硝基酚类污染物的分析测试，为环境中多硝基多酚类物质检测、监控提供了全面、系统的解决方案。液相方法选择全氟苯基色谱柱，以乙腈和乙酸铵+0.1%甲酸作为流动相，梯度洗脱，检测波长为220nm，在优化的固相萃取前处理和液相色谱分离分析条件下，14种硝基酚类化合物在22min内实现完全基线分离，检出限为0.02～0.04mg/kg，回收率达到82.5%～103.8%,相对标准偏差3.2%～5.7%。4.研究建立了超高效液相色谱串联质谱法（QuEChERS UPLC MS/MS）快速、简单、灵敏、准确、廉价和安全地同时测定14种硝基酚类残留量，样品经改进的QuEChERS前处理方法一步完成提取净化。该方法首次实现了14种多硝基酚类物质同时测定的更低的检出限、更高的灵敏度，同时大幅度简化了前处理方法，为更低限量的实验要求建立了更精确的痕量未知污染物确证实验方法。方法经乙腈提取，C18和石墨化炭黑（GCB）吸附剂填料净化，提取液经离心后直接过膜上机检测。UPLC MS/MS方法采用Accucore PFP2.1*150mm i.d.，2.6um色谱柱，柱温30℃，流动相为乙腈和乙酸铵缓冲盐，梯度洗脱，电喷雾电离源负离子模式（ESI）、多反应监测（MRM）模式检测，外标法定量。14种三硝基酚类物质平均加标回收率为76.3%～104.7%；相对标准偏差为3.7%～8.6%；方法的检出限达到0.002～0.005mg/kg。5.通过气相色谱质谱电子轰击源（EI）和液相色谱质谱/质谱电喷雾（ESI）负离子源对多种硝基酚类物质的质谱裂解行为进行了规律分析研究，首次对不同质谱实验数据，首次分析了多种硝基酚类物质的不同结构与相对应的质谱裂解规律和特点，确定了特征裂解碎片，为硝基酚类物质的质谱分析和未知硝基酚化学物质结构解析提供了一定的理论依据。14种硝基酚电喷雾电离（ESI）与电子轰击源（EI）的质谱裂解方式和途径有较大差别，研究结果表明：1)硝基酚类物质在电子轰击源中，具有一定能量的电子流冲击硝基酚类物质分子时，使其失去一个价电子成为带一个正电荷的分子离子M→M+.，硝基酚类化合物基本都有较强的分子离子峰，其裂解过程主要有NO2、NO、CHO、CNO2、OH、CO等自由基的丢失。在化合物中C N键和C O键较易断裂，而且在失去一个NO自由基后，经常伴随着失去一个CO或者CHO自由基的开环反应。而硝基酚类物质酚羟基的特征裂解都有经过H转移丢失CO、CHO，从而产生丢失的M28、M29等基团的碎片。2）硝基酚类物质在电喷雾电离源（ESI）的软电离下，通常较易失去NO、CO、OH、CHO、CNO2、NO2等碎片离子。分子量比较小、分子结构相对简单的一硝基酚通常易失去NO、CO，保持苯环结构。随着硝基和酚羟基数目的增加，在失去NO和OH的时候往往伴随着开环反应，失去一分子C。在结构比较复杂的三硝基酚类物质中，由于键能和空间效应的影响，依次失去NO2碎片离子。6.将微热量热法和热分析法同时用于三硝基酚类在液相色谱担体上的吸附和脱附研究，首次获得的结论给出了液相色谱柱担体分离三硝基酚的分离性和分离速度不同的理论依据，直接为色谱柱担体的选择提供了理论支撑和指导。测量了三种三硝基酚在三类液相色谱柱担体上的吸附热和脱附质量损失数据，获得了相应的热焓和动力学数据，发现含有苯环的PFP担体对三硝基酚类物质的吸附强度大作用强，吸附热大；高温不利于三硝基酚在担体上的吸附，发生的是单分子层吸附，吸附速率小，吸附热高，温度越低，吸附速率增大，吸附过程释放的热量越多，发生的是多分子层吸附；吸附的速率直接影响的是液相色谱分离速度，而吸附热大小决定了分离性的好坏。从而建立色谱柱的选择模式。更多还原

【Abstract】 The Multinitrophenols and its compositions, such as PA、TNR and TNPG, because of itshigh heat sensitivity and high flame sensitivity, easy to ignite, and the characteristics of highoutput energy of the flame, has been widely used in design and production of ignition powder.Environment safety concerns everyone’s health and has attracted more attention around theworld. With the expansion of nitrophenol industrial production, more and more toxicsubstances are expelled to the surroundings, introduced into food chains, and accumulated inhuman bodies. Many of these compounds are carcinogenic, teratogenic and mutagenic toanimals and human. Environment safety has posed a series of life risks for people. Hence, thedevelopment of analysis methods for the determination of toxic substance nitrophenolresidual in environment is necessary to contamination and ensure of environment safety.The main purpose of this thesis was to develop some simple, fast and Cost effectivesample pretreatment methods and analyte concentration methods to analysis of multi residuenitrophenol, The Details in the contents and results of the thesis are as follows:（1） Establish perfect ultrasonic assisted extraction gas chromatography massspectrometry (GC MS) determination of nitrophenol in environment samples, surfacesediments and soil nitrophenol residue analysis method, optimized the extraction method andinstrument analysis conditions. Eight kinds of nitrophenol in0.010～5.0mg/L respectively alinear relationship between concentration scope, correlation coefficient of0.9909, thedetection limit of0.010～0.050mg/kg respectively; Different samples between the averagerecovery was80.6%～115.3%, relative standard deviation is3.4%～10.8%, using thismethod in the water, soil, sediment, obtain the stable recovery.（2） A fast and cost effective method was developed for the determination of multiresidue nitrophenol in environment samples by solid phase extraction. Response surfacemethodology (RSM) and desirability function approach were used to optimize the extractioncondition and evaluate the interaction effect of different parameters in SPE. As a compromiseresult between nitrophenol recovery and pigment clean up degree. A Bond Elut Plexa solidphase extraction(SPE) was used for the extraction and purification of the compounds inenvironmental waste water, the sample loaded was5.0mL,and then eluted with5.0mLAcetonitrile, tetrahydrofuran (4: l), the elution was introduced into the instrument anddetermined by HPLC coupled with photodiode array detector at220nm. A good base line separation of target compounds was obtained in22minutes under the optimum condition ofdetermination. The calibration curves were linear in the concentration range of0.1mg/L～5.0mg/L with correlation coefficients of0.9973～0.9987. Over all recoveries were good(82.5%～105.4%),and the relative standard deviations ranged from3.2%to5.7%for thetarget compounds. The minimum detectable concentrations were0.02mg/kg～0.04mg/kg.This established method is convenient, sensitive and accurate, and was suitable for the routinedetection of trace amide contaminants in environmental samples.（3） A simple, rapid sensitive and accurate ultra performance liquid chromatographytandem mass spectrometry (UPLC MS/MS) method was developed for the simultaneousdetermination of14kinds of nitrophenol residues in environmental samples. The samplepreparation using the modified QuEChERS method completed the extraction and clean upsteps in one procedure. In this none buffer QuEChERS method, samples were cleaned up withprimary graphitized carbon black (GCB) and C18sorbent, then centrifuged and filtratedbefore detection. The pretreatment method was simple, rapid and effective and can meet thedetection requirements. The UPLC MS/MS method was performed on Waters Accucore PFP(2.1*150mm i. d.,2.6m) and the column temperature was30℃, the gradient elution withacetonitrile and ammonium acetate as the mobile phase and the flow rate was0.3mL/min. Thenegative electrospray ionization (ESI) source under the multiple reaction monitoring (MRM)mode and external standard method were used for quantification. The results showed that thecorrelation coefficients up to0.9914were obtained across a concentration range of0.005～0.5mg/L. The limits of detection (LOD) ranged0.002～0.005mg/kg. The method wasvalidated with soil samples spiked at three fortification levels (0.01mg/kg、0.1mg/kg and1mg/kg) and recoveries were in the range of76.3%～104.7%with relative standarddeviations (RSD) of3.7%～8.6%.（4） In this thesis, nitrophenol were chosen to study the ionization and dissociationrules by electron impact and Electro spray ionization tandem mass spectrometer(ESI MS／MS)．It demonstrated that：1) Nitrophenol are prone to form M→M+in EI mode．Fragment ions such as NO2、NO、CHO、CNO2、OH、CO are formed in the dissociation of C O bond, C N bond andrecomposition reaction can also be found．2) Nitrophenol in soft ionization electrospray ionization (ESI), usually more easily lose NO, CO, OH, CHO, CNO2, NO2fragment ions. Smaller molecular weight, molecularstructure relatively simple nitrophenol usually has lost the NO, CO, keep the benzene ringstructure. With the increase of the nitro and nitrophenol hydroxyl number, at the time oflosing NO and OH is often accompanied by ring opening reaction. Trinitrophenol in structureis more complex, because the bond energy and space effects, the influence of the loss of NO2fragment ions in turn.According to MS data, dissociation rule and dissociation characteristic of these14kindsof Nitrophenol chemicals were summarized，which will be a helpful theoretic reference tonitrophenol EI MS and ESI MS/MS analysis and to structural resolution of unknownchemicals．(5)2,4,6Trinitrophenol,2,4,6trinitroresorcinate,2,4,6trinitrophloroglucinol adsorptionheat and mass loss of desorption on stationary phase were tested by micro calorimetry andthermal analysis methods. Corresponding enthalpy and kinetic data were obtained. It was found that theinteraction of adsorption between PFP phase with benzene ring and2,4,6Trinitrophenol,2,4,6trinitroresorcinate,2,4,6Trinitrophloroglucinol were strong and adsorption heat werebig. The high temperature was not favorable to the adsorption of2,4,6Trinitrophenol,2,4,6trinitroresorcinate,2,4,6Trinitrophloroglucinol on phase and the monomolecular layeradsorption was occurred with lower adsorption rate and higher adsorption heat. Multimolecular layer adsorption was occurred with higher adsorption rate and lower adsorptionheat in low temperature environment. Liquid chromatography separate rate was affected byadsorption rate and separate character was decided by adsorption heat.更多还原