新型聚合物整體柱研制及其在毒物分析方面的應(yīng)用
發(fā)布時(shí)間：2019-05-17 21:07
【摘要】：環(huán)境、生物樣品基質(zhì)成分復(fù)雜,且待測物質(zhì)含量較低,測定前,需對目標(biāo)組分進(jìn)行分離、純化和富集等處理,從而提高分析靈敏度和準(zhǔn)確度。聚合物整體柱微萃取(Polymer monolithic column microextraction,PMME)技術(shù)是一種溶劑用量少的管內(nèi)固相微萃取技術(shù),具有操作簡單、耗時(shí)少、效率高等優(yōu)點(diǎn),萃取介質(zhì)是PMME技術(shù)的關(guān)鍵。目前,聚合物整體柱材料的種類有限,仍難滿足不同性質(zhì)復(fù)雜樣品中痕量目標(biāo)物的分析需求,需發(fā)展新型高效的萃取介質(zhì)。本文開展了新型聚合物整體柱的研制,及其在復(fù)雜樣品中痕量目標(biāo)物富集分離中的應(yīng)用研究。主要研究內(nèi)容如下:1.概述了固相微萃取技術(shù)研究進(jìn)展;介紹了整體柱在樣品前處理中的應(yīng)用;詳細(xì)論述了聚合物整體柱分類、制備、功能化現(xiàn)狀,及其在樣品前處理技術(shù)中的應(yīng)用進(jìn)展。2.開展了聚(甲基丙烯酸-二甲基丙烯酸乙二醇酯-N-乙烯咔唑)(poly(MAA-EGDMA-NVC))毛細(xì)管整體柱的制備及其應(yīng)用研究。采用熱引發(fā)原位聚合法制備poly(MAA-EDMA-NVC)整體柱,該柱結(jié)構(gòu)均勻、多孔通透、穩(wěn)定性良好,使用100次后萃取性能無明顯下降。利用N-乙烯咔唑穩(wěn)定、極性、含有π共軛結(jié)構(gòu)的特點(diǎn),將NVC修飾poly(MAA-EDMA)整體柱可增強(qiáng)該聚合物柱對3種苯二氮卓類藥物(BZPs)的富集能力,對BZPs的富集因子為59.2 68.1。建立了poly(MAA-EGDMA-NVC)聚合物整體柱萃取與氣相色譜(GC)聯(lián)用測定BZPs藥物的分析方法,該方法線性范圍為0.1 50 ng/m L,相關(guān)系數(shù)R2≥0.9965。檢出限(S/N=3)為0.011 0.026 ng/m L,定量限(S/N=10)為0.036 0.088 ng/mL。該方法用于尿液和啤酒中BZPs藥物的分析,加標(biāo)回收率分別為81.4 93.3%和83.3 94.7%,RSDs分別為4.1 8.1%和3.8 8.5%。該方法為復(fù)雜樣品內(nèi)痕量藥物分析提供了的簡便、精確、精密度高的分析方法。3.開展了聚(N-乙烯咔唑-二乙烯基苯)(poly(NVC-DVB))毛細(xì)管整體柱的制備及應(yīng)用研究。采用熱引發(fā)原位聚合法制備聚合物整體柱,制備過程中對致孔劑含量進(jìn)行優(yōu)化,得到結(jié)構(gòu)均勻,連續(xù)多孔,通透性和穩(wěn)定性良好,使用壽命長的poly(NVC-DVB)整體柱。該柱含有豐富的π電子和通透性較好的多孔結(jié)構(gòu),可通過π-π作用吸附BZPs藥物。建立了poly(NVC-DVB)整體柱萃取與高效液相色譜/Q-Orbitrap質(zhì)譜(HPLC/MS)聯(lián)用測定6種BZPs藥物的分析方法,勞拉西泮的線性范圍為0.01 0.5 ng/mL,硝西泮的線性范圍為0.05 0.5 ng/mL,艾司唑侖、氯氮卓、阿普唑侖和咪達(dá)唑侖的線性范圍為0.05 0.5 ng/mL,相關(guān)系數(shù)R2≥0.9991。檢出限為1.08 6.04 ng/L,定量限為3.60 20.1ng/L。該方法用于尿液和啤酒中6種BZPs藥物的分析,加標(biāo)回收率分別為79.6 95.2%和80.5 94.2%。該方法簡便、靈敏,能夠滿足實(shí)際樣品中痕量藥物的分析需求,具有重要的實(shí)際意義。4.以poly(NVC-DVB)為載體,開展了石墨烯毛細(xì)管整體柱的制備及應(yīng)用研究。制備過程中優(yōu)化了石墨烯的含量,得到結(jié)構(gòu)穩(wěn)定、均勻和通透性好的三維石墨烯整體柱,該柱集合單層石墨烯和多孔poly(NVC-DVB)兩者的優(yōu)勢。根據(jù)石墨烯比表面積大、富π電子和穩(wěn)定高的特點(diǎn),石墨烯加入后提高了整體柱對6種BZPs的萃取性能。建立了石墨烯整體柱萃取與HPLC/MS聯(lián)用測定6種BZPs藥物的分析方法,得出硝西泮、艾司唑侖、氯氮卓和阿普唑侖的線性范圍為0.005 1 ng/mL,勞拉西泮和咪達(dá)唑侖的線性范圍為0.01 1 ng/m L,相關(guān)系數(shù)R2≥0.9986。檢出限為1.12 2.35 ng/L,定量限為3.74 7.83ng/L。該方法用于生物樣品尿液和頭發(fā)中BZPs藥物的分析,加標(biāo)回收率為分別為8.6 85.6%和87.2 94.3%,RSDs分別為3.4 6.9%和2.9 8.3%。結(jié)果證明該方法為生物樣品中藥物分析提供了靈敏可靠的方法。5.開展了UiO-66/poly(NVC-DVB)毛細(xì)管整體柱的制備及應(yīng)用研究。UiO-66是由Zr4+與對苯二甲酸構(gòu)建的一種金屬有機(jī)骨架材料,具有熱穩(wěn)定性和機(jī)械穩(wěn)定性高,耐有機(jī)溶劑、耐酸堿,比表面積高等優(yōu)點(diǎn)。在poly(NVC-DVB)聚合物整體中引入U(xiǎn)iO-66,通過優(yōu)化UiO-66含量,得到穩(wěn)定、均勻和通透性好的UiO-66/poly(NVC-DVB)整體柱。與poly(NVC-DVB)整體柱相比,提高了對三唑類殺菌劑的富集性能。建立了UiO-66/poly(NVC-DVB)聚合物整體柱萃取與HPLC/MS聯(lián)用測定三唑類殺菌劑的分析方法,得到嘧霉胺線性范圍為0.005 1 ng/m L,粉唑醇線性范圍為0.01 1 ng/mL,戊唑醇、己唑醇和烯唑醇線性范圍為0.05-1 ng/mL,相關(guān)系數(shù)R2≥0.9911。檢出限的范圍為1.34 14.8 ng/L,定量限為4.45 49.4 ng/L。該方法用于環(huán)境水和土壤中三唑類殺菌劑的分析,加標(biāo)回收率為90.4 97.5%和84.0 95.3%。能夠滿足復(fù)雜環(huán)境樣品內(nèi)痕量殺菌劑分析的要求。
[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.
【學(xué)位授予單位】：山西師范大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O658.2
本文編號：2479408
[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.
【學(xué)位授予單位】：山西師范大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O658.2
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