有機(jī)改性氣凝膠涂層用于管內(nèi)固相微萃取的研究
發(fā)布時(shí)間：2019-05-27 05:36
【摘要】：樣品基質(zhì)復(fù)雜、待測(cè)組分的含量較低等因素促使樣品前處理成為樣品分析的關(guān)鍵環(huán)節(jié)。有效的樣品前處理技術(shù)可以降低雜質(zhì)的干擾,濃縮痕量組分,提高分析方法的靈敏度。固相微萃取是一種集采樣、萃取、濃縮、進(jìn)樣于一體的樣品前處理技術(shù),具有操作簡(jiǎn)便,精確度高,易于與分析儀器聯(lián)用實(shí)現(xiàn)在線分析等優(yōu)點(diǎn)。常規(guī)固相微萃取適用于與氣相色譜聯(lián)用檢測(cè)沸點(diǎn)低、熱穩(wěn)定性高的分析物,但對(duì)于大多數(shù)沸點(diǎn)高,熱不穩(wěn)定性分析物難以實(shí)現(xiàn)有效富集分析。管內(nèi)固相微萃取可以方便與高效液相色譜聯(lián)用,實(shí)現(xiàn)對(duì)大部分目標(biāo)分析物有效的萃取與分析。纖維填充型管內(nèi)固相微萃取是一種獨(dú)特的管內(nèi)固相微萃取形式,它不僅增大了涂層面積,而且降低管內(nèi)死體積,有效改善峰形,增加萃取效率并提高分析準(zhǔn)確度。但目前涂層種類有限、選擇性差、使用壽命短是制約纖維管內(nèi)固相微萃取的主要因素。氣凝膠是一種性質(zhì)十分優(yōu)異的納米三維立體網(wǎng)絡(luò)多孔材料,其巨大的比表面積及豐富的種類使其在在管內(nèi)固相微萃取方面具有良好的應(yīng)用潛力。本論文將氣凝膠材料進(jìn)行有機(jī)功能化改性,在玄武巖纖維和鈦絲表面制備有機(jī)改性氣凝膠涂層,將其置于PEEK管內(nèi)制備出管內(nèi)固相微萃取裝置,與液相色譜在線聯(lián)用實(shí)現(xiàn)在線富集分析環(huán)境中常見的多環(huán)芳烴和環(huán)境雌激素等重要污染物。主要研究?jī)?nèi)容及結(jié)果如下:1.以綠色環(huán)保的玄武巖纖維為基體,在其表面制備間苯二酚改性的三聚氰胺氣凝膠作為萃取涂層,置于PEEK管內(nèi)制備出管內(nèi)固相微萃取裝置,并對(duì)涂層進(jìn)行了掃描電鏡及紅外光譜表征。選擇多類物質(zhì)考察了涂層的萃取選擇性,選擇萃取效率最高的8種多環(huán)芳烴作為模型分析物,分別對(duì)萃取流速、體積、有機(jī)溶劑含量、離子強(qiáng)度、pH值和脫附時(shí)間進(jìn)行了優(yōu)化。在最佳條件下,得出各物質(zhì)的檢測(cè)限在0.01-0.05μg L-1之間,線性范圍為0.03-100μg L-1,日內(nèi)與日間重現(xiàn)性相對(duì)標(biāo)準(zhǔn)偏差在1.9-3.9%和3.9-7.4%之間,并成功應(yīng)用于實(shí)際水樣中多環(huán)芳烴的分析檢測(cè)。2.在玄武巖纖維表面制備對(duì)苯二甲醛改性的二氧化硅氣凝膠萃取涂層,裝填萃取管,對(duì)涂層及纖維基體進(jìn)行了掃描電鏡及紅外光譜表征。與液相色譜在線聯(lián)用考察了萃取選擇性,以5種環(huán)境雌激素為模型分析物,對(duì)萃取流速、體積、有機(jī)溶劑含量、離子強(qiáng)度、pH值和脫附時(shí)間等影響萃取效率的因素進(jìn)行了優(yōu)化。在最優(yōu)條件下,各物質(zhì)的檢測(cè)限在0.01-0.05μg L-1之間,線性范圍為0.06-100μg L-1,富集倍數(shù)在2364-3132之間。該方法被成功應(yīng)用于對(duì)實(shí)際樣品中雌激素的分析。3.利用聚氨酯改性的二氧化硅氣凝膠涂層對(duì)玄武巖纖維進(jìn)行功能化,裝填PEEK管制得固相微萃取裝置。以環(huán)境雌激素作為模型分析物,分別考察了萃取流速、樣品體積、有機(jī)溶劑含量、離子強(qiáng)度、pH值和脫附時(shí)間對(duì)萃取及洗脫效率的影響。在最佳條件下,各物質(zhì)工作曲線的線性系數(shù)在0.9991-0.9998之間,線性范圍為在0.10-50μg L-1和0.03-100μg L-1之間,檢測(cè)限在0.01-0.03μg L-1之間,所建立的分析方法應(yīng)用到實(shí)際樣品的檢測(cè)。4.以鈦絲為基體,制備聚多巴胺改性的氧化石墨烯氣凝膠作為萃取涂層裝填PEEK管得到固相微萃取管,考察了萃取與洗脫條件。在最佳條件下,得出各物質(zhì)的線性范圍為0.03-50μg L-1,檢出限最低達(dá)到0.01μg L-1,萃取重現(xiàn)性的相對(duì)標(biāo)準(zhǔn)偏差在0.77-3.65%之間,萃取管的制備重現(xiàn)性相對(duì)標(biāo)準(zhǔn)偏差低于5%,成功應(yīng)用于對(duì)食品盒,煤灰樣品的檢測(cè),表明該萃取材料在管內(nèi)固相微萃取方面具有良好的應(yīng)用價(jià)值。
[Abstract]:The sample matrix is complex, the content of the component to be tested is lower, and the pretreatment of the sample is the key link of the sample analysis. The effective sample pretreatment technology can reduce the interference of impurities, concentrate trace components, and improve the sensitivity of the analytical method. Solid-phase microextraction is a kind of pre-sample processing technique for sampling, extraction, concentration and injection. It has the advantages of simple and convenient operation, high precision, and easy to be combined with analytical instrument to realize on-line analysis. The conventional solid-phase microextraction is suitable for the analysis of low boiling point and high thermal stability in combination with gas chromatography, but for most of the high boiling point, the thermal instability analysis is difficult to realize the effective enrichment analysis. The solid-phase micro-extraction in the tube can be conveniently combined with high performance liquid chromatography to achieve the effective extraction and analysis of most of the target analytes. The solid-phase microextraction in a fiber-filled tube is a unique form of solid-phase micro-extraction in a tube, which not only increases the area of the coating, but also reduces the dead volume in the tube, effectively improves the peak shape, increases the extraction efficiency and improves the analysis accuracy. However, the coating types are limited, the selectivity is poor, and the short service life is the main factor to restrict the solid-phase micro-extraction in the fiber tube. Aerogel is a kind of three-dimensional, three-dimensional, three-dimensional network porous material with very excellent properties, and its large specific surface area and rich species make it have good application potential in solid-phase micro-extraction in the tube. The method comprises the following steps of: carrying out organic functional modification on the aerogel material, preparing an organic modified aerogel coating on the surface of the basalt fiber and the titanium wire, and placing the organic modified aerogel coating in the PEEK tube to prepare the solid-phase micro-extraction device in the tube; And can realize on-line enrichment and analysis of important pollutants such as polycyclic aromatic hydrocarbons and environmental estrogens in an on-line enrichment analysis environment by using the liquid chromatography on-line. The main contents and results are as follows:1. Based on the green and environment-friendly basalt fiber, a resorcinol-modified melamine aerogel is prepared as an extraction coating on the surface of the base, and a solid-phase micro-extraction device in the tube is prepared in the PEEK tube, and the coating is characterized by scanning electron microscopy and infrared spectroscopy. The extraction rate, volume, organic solvent content, ionic strength, pH value and desorption time were optimized. Under the best condition, the detection limit of each substance is between 0.01 and 0.05. mu. g L-1, the linear range is 0.03-100 & mu; g L-1, the relative standard deviation of the intra-day and the day reproducibility is 1.9-3.9% and 3.9-7.4%, and the detection of the polycyclic aromatic hydrocarbon in the real water sample is successfully applied. A modified silica aerogel extraction coating was prepared on the surface of the basalt fiber, the extraction tube was filled, and the coating and the fiber matrix were characterized by scanning electron microscope and infrared spectroscopy. The factors such as extraction flow rate, volume, organic solvent content, ionic strength, pH value and desorption time were optimized by on-line combination with liquid chromatography. Under the optimal conditions, the detection limit of each substance is between 0.01 and 0.05. mu; g L-1, the linear range is 0.06-100 & mu; g L-1, and the enrichment factor is between 2364 and 3132. The method was successfully applied to the analysis of the estrogen in the actual sample. The basalt fiber is functionalized with a polyurethane modified silica aerogel coating, and the solid phase micro-extraction device is filled with PEEK. The effects of extraction flow rate, sample volume, organic solvent content, ionic strength, pH value and desorption time on the extraction and elution efficiency were investigated. Under the best conditions, the linear coefficient of the working curve of each substance is between 0.9991 and 0.9998, the linear range is between 0.10-50 & mu; g L-1 and 0.03-100 & mu; g L-1, the detection limit is between 0.01-0.03 & mu; g L-1, and the established analytical method is applied to the detection of the actual sample. A solid-phase micro-extraction tube was prepared by using the titanium wire as a matrix to prepare the polydopamine-modified graphene oxide aerogel as an extraction coating, and the extraction and elution conditions were investigated. Under the best condition, the linear range of each substance is 0.03-50 & mu; g L-1, the detection limit is at least 0.01 & mu; g L-1, the relative standard deviation of the extraction reproducibility is between 0.77 and 3.65%, the relative standard deviation of the extraction tube is less than 5%, and the extraction tube is successfully applied to the food box, The detection of the coal ash sample shows that the extraction material has good application value in the solid-phase micro-extraction of the tube.
【學(xué)位授予單位】：濟(jì)南大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O658.2
本文編號(hào)：2485932
[Abstract]:The sample matrix is complex, the content of the component to be tested is lower, and the pretreatment of the sample is the key link of the sample analysis. The effective sample pretreatment technology can reduce the interference of impurities, concentrate trace components, and improve the sensitivity of the analytical method. Solid-phase microextraction is a kind of pre-sample processing technique for sampling, extraction, concentration and injection. It has the advantages of simple and convenient operation, high precision, and easy to be combined with analytical instrument to realize on-line analysis. The conventional solid-phase microextraction is suitable for the analysis of low boiling point and high thermal stability in combination with gas chromatography, but for most of the high boiling point, the thermal instability analysis is difficult to realize the effective enrichment analysis. The solid-phase micro-extraction in the tube can be conveniently combined with high performance liquid chromatography to achieve the effective extraction and analysis of most of the target analytes. The solid-phase microextraction in a fiber-filled tube is a unique form of solid-phase micro-extraction in a tube, which not only increases the area of the coating, but also reduces the dead volume in the tube, effectively improves the peak shape, increases the extraction efficiency and improves the analysis accuracy. However, the coating types are limited, the selectivity is poor, and the short service life is the main factor to restrict the solid-phase micro-extraction in the fiber tube. Aerogel is a kind of three-dimensional, three-dimensional, three-dimensional network porous material with very excellent properties, and its large specific surface area and rich species make it have good application potential in solid-phase micro-extraction in the tube. The method comprises the following steps of: carrying out organic functional modification on the aerogel material, preparing an organic modified aerogel coating on the surface of the basalt fiber and the titanium wire, and placing the organic modified aerogel coating in the PEEK tube to prepare the solid-phase micro-extraction device in the tube; And can realize on-line enrichment and analysis of important pollutants such as polycyclic aromatic hydrocarbons and environmental estrogens in an on-line enrichment analysis environment by using the liquid chromatography on-line. The main contents and results are as follows:1. Based on the green and environment-friendly basalt fiber, a resorcinol-modified melamine aerogel is prepared as an extraction coating on the surface of the base, and a solid-phase micro-extraction device in the tube is prepared in the PEEK tube, and the coating is characterized by scanning electron microscopy and infrared spectroscopy. The extraction rate, volume, organic solvent content, ionic strength, pH value and desorption time were optimized. Under the best condition, the detection limit of each substance is between 0.01 and 0.05. mu. g L-1, the linear range is 0.03-100 & mu; g L-1, the relative standard deviation of the intra-day and the day reproducibility is 1.9-3.9% and 3.9-7.4%, and the detection of the polycyclic aromatic hydrocarbon in the real water sample is successfully applied. A modified silica aerogel extraction coating was prepared on the surface of the basalt fiber, the extraction tube was filled, and the coating and the fiber matrix were characterized by scanning electron microscope and infrared spectroscopy. The factors such as extraction flow rate, volume, organic solvent content, ionic strength, pH value and desorption time were optimized by on-line combination with liquid chromatography. Under the optimal conditions, the detection limit of each substance is between 0.01 and 0.05. mu; g L-1, the linear range is 0.06-100 & mu; g L-1, and the enrichment factor is between 2364 and 3132. The method was successfully applied to the analysis of the estrogen in the actual sample. The basalt fiber is functionalized with a polyurethane modified silica aerogel coating, and the solid phase micro-extraction device is filled with PEEK. The effects of extraction flow rate, sample volume, organic solvent content, ionic strength, pH value and desorption time on the extraction and elution efficiency were investigated. Under the best conditions, the linear coefficient of the working curve of each substance is between 0.9991 and 0.9998, the linear range is between 0.10-50 & mu; g L-1 and 0.03-100 & mu; g L-1, the detection limit is between 0.01-0.03 & mu; g L-1, and the established analytical method is applied to the detection of the actual sample. A solid-phase micro-extraction tube was prepared by using the titanium wire as a matrix to prepare the polydopamine-modified graphene oxide aerogel as an extraction coating, and the extraction and elution conditions were investigated. Under the best condition, the linear range of each substance is 0.03-50 & mu; g L-1, the detection limit is at least 0.01 & mu; g L-1, the relative standard deviation of the extraction reproducibility is between 0.77 and 3.65%, the relative standard deviation of the extraction tube is less than 5%, and the extraction tube is successfully applied to the food box, The detection of the coal ash sample shows that the extraction material has good application value in the solid-phase micro-extraction of the tube.
【學(xué)位授予單位】：濟(jì)南大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O658.2
【參考文獻(xiàn)】
相關(guān)期刊論文 前10條
1 彭英;莊園;何歡;孫成;楊紹貴;;硫酸改性聚(甲基丙烯酸縮水甘油酯-乙二醇二甲基丙烯酸酯)固相微萃取涂層-高效液相色譜檢測(cè)水中4種藥品及個(gè)人護(hù)理用品[J];分析化學(xué);2014年09期
2 饒思奇;回琳;鄧敏;徐祖順;張全元;;甲基丙烯酸縮水甘油酯交聯(lián)殼聚糖/聚乙烯醇水凝膠薄膜的制備及性能[J];材料科學(xué)與工程學(xué)報(bào);2014年04期
3 李海芳;楊紅云;張英;王培龍;林金明;;四氧化三鐵/單壁碳納米管磁性復(fù)合納米粒子分散固相微萃取-高效液相色譜法測(cè)定牛奶中的香精添加劑[J];色譜;2014年04期
4 胡艷云;徐慧群;姚劍;呂亞寧;宋偉;李文靜;韓芳;鄭平;;分子印跡固相萃取-液相色譜-質(zhì)譜法測(cè)定果蔬中20種三唑類農(nóng)藥殘留[J];分析化學(xué);2014年02期
5 劉光明;楊曉東;林繼月;田繼紅;;MTES含量對(duì)Al_2O_3/有機(jī)硅/SiO_2雜化涂層性能的影響[J];材料研究學(xué)報(bào);2012年04期
6 許志剛;胡玉玲;李攻科;;攪拌棒吸附萃取技術(shù)的研究進(jìn)展[J];分析化學(xué);2011年11期
7 李文超;王永花;孫成;楊紹貴;;分子印跡技術(shù)與固相微萃取技術(shù)聯(lián)用的研究進(jìn)展[J];環(huán)境化學(xué);2011年09期
8 林宇巍;;毛細(xì)管內(nèi)固相微萃取技術(shù)的研究進(jìn)展[J];福建分析測(cè)試;2011年03期
9 胡培亮;方定琴;趙廣超;;殼聚糖/SiO_2/CdS納米復(fù)合物作為固相萃取膜測(cè)定環(huán)境水樣中的有機(jī)磷農(nóng)藥殘留[J];合肥師范學(xué)院學(xué)報(bào);2010年06期
10 王博;黃劍鋒;夏�？�;;電化學(xué)沉積法制備薄膜、涂層材料研究進(jìn)展[J];陶瓷;2010年01期
相關(guān)會(huì)議論文 前1條
1 王寧;昌霞;陳杰;李晶晶;馮江濤;延衛(wèi);;聚苯胺/TiO_2復(fù)合吸附劑的制備及對(duì)染料的吸附性能研究[A];2014中國(guó)環(huán)境科學(xué)學(xué)會(huì)學(xué)術(shù)年會(huì)論文集（第五章）[C];2014年
，本文編號(hào)：2485932
本文鏈接：http://sikaile.net/kejilunwen/huaxue/2485932.html
最近更新
教材專著
