新型聚合物整体柱研制及其在毒物分析方面的应用

发布时间：2019-05-17 21:07

【摘要】：环境、生物样品基质成分复杂,且待测物质含量较低,测定前,需对目标组分进行分离、纯化和富集等处理,从而提高分析灵敏度和准确度。聚合物整体柱微萃取(Polymer monolithic column microextraction,PMME)技术是一种溶剂用量少的管内固相微萃取技术,具有操作简单、耗时少、效率高等优点,萃取介质是PMME技术的关键。目前,聚合物整体柱材料的种类有限,仍难满足不同性质复杂样品中痕量目标物的分析需求,需发展新型高效的萃取介质。本文开展了新型聚合物整体柱的研制,及其在复杂样品中痕量目标物富集分离中的应用研究。主要研究内容如下:1.概述了固相微萃取技术研究进展;介绍了整体柱在样品前处理中的应用;详细论述了聚合物整体柱分类、制备、功能化现状,及其在样品前处理技术中的应用进展。2.开展了聚(甲基丙烯酸-二甲基丙烯酸乙二醇酯-N-乙烯咔唑)(poly(MAA-EGDMA-NVC))毛细管整体柱的制备及其应用研究。采用热引发原位聚合法制备poly(MAA-EDMA-NVC)整体柱,该柱结构均匀、多孔通透、稳定性良好,使用100次后萃取性能无明显下降。利用N-乙烯咔唑稳定、极性、含有π共轭结构的特点,将NVC修饰poly(MAA-EDMA)整体柱可增强该聚合物柱对3种苯二氮卓类药物(BZPs)的富集能力,对BZPs的富集因子为59.2 68.1。建立了poly(MAA-EGDMA-NVC)聚合物整体柱萃取与气相色谱(GC)联用测定BZPs药物的分析方法,该方法线性范围为0.1 50 ng/m L,相关系数R2≥0.9965。检出限(S/N=3)为0.011 0.026 ng/m L,定量限(S/N=10)为0.036 0.088 ng/mL。该方法用于尿液和啤酒中BZPs药物的分析,加标回收率分别为81.4 93.3%和83.3 94.7%,RSDs分别为4.1 8.1%和3.8 8.5%。该方法为复杂样品内痕量药物分析提供了的简便、精确、精密度高的分析方法。3.开展了聚(N-乙烯咔唑-二乙烯基苯)(poly(NVC-DVB))毛细管整体柱的制备及应用研究。采用热引发原位聚合法制备聚合物整体柱,制备过程中对致孔剂含量进行优化,得到结构均匀,连续多孔,通透性和稳定性良好,使用寿命长的poly(NVC-DVB)整体柱。该柱含有丰富的π电子和通透性较好的多孔结构,可通过π-π作用吸附BZPs药物。建立了poly(NVC-DVB)整体柱萃取与高效液相色谱/Q-Orbitrap质谱(HPLC/MS)联用测定6种BZPs药物的分析方法,劳拉西泮的线性范围为0.01 0.5 ng/mL,硝西泮的线性范围为0.05 0.5 ng/mL,艾司唑仑、氯氮卓、阿普唑仑和咪达唑仑的线性范围为0.05 0.5 ng/mL,相关系数R2≥0.9991。检出限为1.08 6.04 ng/L,定量限为3.60 20.1ng/L。该方法用于尿液和啤酒中6种BZPs药物的分析,加标回收率分别为79.6 95.2%和80.5 94.2%。该方法简便、灵敏,能够满足实际样品中痕量药物的分析需求,具有重要的实际意义。4.以poly(NVC-DVB)为载体,开展了石墨烯毛细管整体柱的制备及应用研究。制备过程中优化了石墨烯的含量,得到结构稳定、均匀和通透性好的三维石墨烯整体柱,该柱集合单层石墨烯和多孔poly(NVC-DVB)两者的优势。根据石墨烯比表面积大、富π电子和稳定高的特点,石墨烯加入后提高了整体柱对6种BZPs的萃取性能。建立了石墨烯整体柱萃取与HPLC/MS联用测定6种BZPs药物的分析方法,得出硝西泮、艾司唑仑、氯氮卓和阿普唑仑的线性范围为0.005 1 ng/mL,劳拉西泮和咪达唑仑的线性范围为0.01 1 ng/m L,相关系数R2≥0.9986。检出限为1.12 2.35 ng/L,定量限为3.74 7.83ng/L。该方法用于生物样品尿液和头发中BZPs药物的分析,加标回收率为分别为8.6 85.6%和87.2 94.3%,RSDs分别为3.4 6.9%和2.9 8.3%。结果证明该方法为生物样品中药物分析提供了灵敏可靠的方法。5.开展了UiO-66/poly(NVC-DVB)毛细管整体柱的制备及应用研究。UiO-66是由Zr4+与对苯二甲酸构建的一种金属有机骨架材料,具有热稳定性和机械稳定性高,耐有机溶剂、耐酸碱,比表面积高等优点。在poly(NVC-DVB)聚合物整体中引入UiO-66,通过优化UiO-66含量,得到稳定、均匀和通透性好的UiO-66/poly(NVC-DVB)整体柱。与poly(NVC-DVB)整体柱相比,提高了对三唑类杀菌剂的富集性能。建立了UiO-66/poly(NVC-DVB)聚合物整体柱萃取与HPLC/MS联用测定三唑类杀菌剂的分析方法,得到嘧霉胺线性范围为0.005 1 ng/m L,粉唑醇线性范围为0.01 1 ng/mL,戊唑醇、己唑醇和烯唑醇线性范围为0.05-1 ng/mL,相关系数R2≥0.9911。检出限的范围为1.34 14.8 ng/L,定量限为4.45 49.4 ng/L。该方法用于环境水和土壤中三唑类杀菌剂的分析,加标回收率为90.4 97.5%和84.0 95.3%。能够满足复杂环境样品内痕量杀菌剂分析的要求。
[Abstract]:In that environment, the matrix component of the biological sample is complex, and the content of the substance to be tested is low, and before the measurement, the target component is separated, purified and enriched, and the like so as to improve the analysis sensitivity and the accuracy. Polymer monolithic column microextraction (PME) is a solid-phase micro-extraction technology in a tube with less solvent consumption. It has the advantages of simple operation, less time consumption, high efficiency and the like, and the extraction medium is the key to the PME technology. At present, the types of polymer monolithic column materials are limited, and it is still difficult to meet the analysis demand of trace target in complex samples with different properties, and a new type of high-efficiency extraction medium needs to be developed. The development of a novel polymer monolithic column and its application in the enrichment and separation of trace target in complex samples are studied in this paper. The main contents of the study are as follows:1. In this paper, the progress of solid-phase microextraction is summarized, the application of the monolithic column in the pretreatment of the sample is introduced, the classification, preparation and functional status of the polymer monolithic column are discussed in detail, and the application progress of the whole column in the pretreatment of the sample is discussed in detail. The preparation and application of poly (MAA-EGDMA-NVC) capillary whole column were carried out. A poly (MAA-EDMA-NVC) monolithic column was prepared by heat-induced in-situ polymerization. The column was uniform in structure, porous and transparent, with good stability and no significant decrease in the extraction performance after 100 times. NVC modified poly (MAA-EDMA) monolithic column can enhance the enrichment ability of 3 kinds of benzodiazepines (BZPs), and the enrichment factor of BZPs is 59.2.68. A poly (MAA-EGDMA-NVC) polymer monolithic column extraction and gas chromatography (GC) method for the determination of BZPs drug was established. The linear range of the method was 0.1 50 ng/ m L, and the correlation coefficient R2 was 0.9965. The detection limit (S/ N = 3) was 0.011 0.026 ng/ m L and the limit of quantification (S/ N = 10) was 0.036 0.088 ng/ mL. The recoveries of BZPs in urine and beer were 81.4 93.3% and 83.3 94.7%, and the RSDs were 4.1.1% and 3.8.5%, respectively. The method provides a simple, accurate and high-precision analysis method for trace drug analysis in complex samples. The preparation and application of poly (N-vinylbenzene-divinylbenzene) (poly (NVC-DVB) capillary whole column were carried out. The polymer monolithic column is prepared by adopting a heat-induced in-situ polymerization method, and the content of the pore-forming agent is optimized in the preparation process to obtain a poly (NVC-DVB) monolithic column with the advantages of uniform structure, continuous porosity, good permeability and stability and long service life. The column contains a rich porous structure with good electron and permeability, and can be used for adsorbing the BZPs drug through the action of the carbon dioxide. The method of determination of six kinds of BZPs with high performance liquid chromatography/ Q-Orbitrap mass spectrometry (HPLC/ MS) with poly (NVC-DVB) whole column extraction and high performance liquid chromatography/ Q-Orbitrap mass spectrometry (HPLC/ MS) was established. The linear range of apperylene and prochlorphenram was 0.05 ng/ mL, and the correlation coefficient R2 was 0.9991. The detection limit was 1.08 6.04 ng/ L and the limit of quantitation was 3.60. 20.1 ng/ L. The method is used for the analysis of six kinds of BZPs in urine and beer, and the recovery rate is 79.6 95.2% and 80.5 94.2%, respectively. The method is simple and sensitive, can meet the analysis requirement of trace drugs in the actual sample, and has important practical significance. With poly (NVC-DVB) as the carrier, the preparation and application of the graphene capillary whole column were carried out. The content of the graphene is optimized in the preparation process, so that the three-dimensional graphene monolithic column with stable structure, uniform and permeability is obtained, and the column is an advantage of both the single-layer graphene and the porous poly (NVC-DVB). According to the characteristics of large specific surface area of the graphene, rich and stable electrons and high stability, the graphene is added, and the extraction performance of the whole column on the six kinds of BZPs is improved. The analytical methods of 6 kinds of BZPs were determined by the combination of the whole column of graphene and the HPLC/ MS. The linear range of the linear range of the nitrosipelas, escitalopram, chlordiazepin and apperylene was 0.005 1 ng/ mL, and the linear range of Rasidone and Mimidamylene was 0.01 1 ng/ mL, and the correlation coefficient of R2 was 0.9986. The detection limit was 1.12 2.35 ng/ L and the limit of quantification was 3.74 7.83 ng/ L. The method was used in the analysis of the drug of BZPs in the urine and hair of the biological sample. The recovery rate was 8.6 85.6% and 87.2 94.3%, respectively, and the RSDs were 3.4.9% and 2.9.3%, respectively. The results show that the method provides a sensitive and reliable method for drug analysis in biological samples. The preparation and application of UiO-66/ poly (NVC-DVB) capillary whole column were carried out. UiO-66 is a kind of metal organic framework material constructed from Zr4 + and terephthalic acid, and has the advantages of high thermal stability and mechanical stability, organic solvent resistance, acid and alkali resistance, specific surface area and the like. UiO-66 was introduced in a poly (NVC-DVB) polymer, and the UiO-66/ poly (NVC-DVB) monolithic column was obtained by optimizing the UiO-66 content. Compared with the poly (NVC-DVB) monolithic column, the enrichment performance of the three-class bactericide is improved. The analytical method of UiO-66/ poly (NVC-DVB) polymer whole column extraction and HPLC/ MS was established to determine the three-class germicide. The linear range of the mycophenamine was 0.005 1 ng/ m L, the linear range of the prostenol was 0.01 1 ng/ mL, the linear range of the pentanol, the hexanyl alcohol and the allyl alcohol was 0.05 -1 ng/ mL, and the correlation coefficient R2 was 0.9911. The limit of detection was 1.34 14.8 ng/ L and the limit of quantitation was 4.45 49.4 ng/ L. The method is used for the analysis of the three-class bactericide in the environment water and the soil, and the recovery rate of the spike is 90.4 97.5% and 84.0 95.3%. And can meet the requirement of trace bactericide analysis in a complex environment sample.
【学位授予单位】：山西师范大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O658.2

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